HYDROTREATMENT CATALYSTS AND PROCESS FOR PREPARING SAID CATALYSTS

Abstract

The present invention is in the field of heterogeneous catalysis.

Particularly, the present invention relates to a process for preparing catalysts advantageously usable in the hydrotreatment processes, for example in hydrodesulphurization, hydrodenitrogenation, hydrodearomatization processes of hydrocarbons.

More in particular, the present invention relates to a process for obtaining said catalysts, which comprise mixed oxides of Nickel, Aluminum, Molybdenum and Tungsten and optionally a transition metal Me selected from the group consisting of Zn, Mn, Cd, and a mixture thereof, an organic component C, and possibly an inorganic binder B.

Said mixed oxides comprise an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite.

The present invention further relates to said hydrotreatment catalysts and a hydrotreatment process wherein said catalysts are used.

Claims

1. A metal sulphide catalyst obtained by sulphidation of the mixed oxide of formula (I) or of the mixed oxide of formula (I) bound to at least one inorganic binder B, wherein formula (I) is as follows
Me.sub.aNi.sub.bMo.sub.cW.sub.dAl.sub.eO.sub.f.pC  (I), wherein: Me is selected from the group consisting of Zn, Cd, Mn, and a mixture thereof, C comprises a polymer organic compound, a is higher than or equal to 0, b, c, d, e and f are higher than 0, f is equal to (2a+2b+6c+6d+3e)/2, the (a+b)/(c+d) ratio is 0.9 to 1.1, the a/b ratio is 0 to 1.5, the c/d ratio is 0.2 to 5, the (a+b+c+d)/e ratio is 0.6 to 5, and p is the weight percentage of C with respect to the total weight of the mixed oxide of formula (I), and is higher than 0% and lower than or equal to 40%, said mixed oxide of formula (I) comprising an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite.

2. A process of hydrotreating of a feed containing one or more hydrocarbons which comprises contacting said feed with hydrogen in the presence of the catalyst of claim 1.

3. A process for obtaining a mixed oxide of claim 1, comprising Ni, Mo, W, Al, optionally at least one metal Me and an organic component C or a residue of said organic component C, having the following formula (I)
Me.sub.aNi.sub.bMo.sub.cW.sub.dAl.sub.eO.sub.f.pC  (I), wherein; to Me is selected from the group consisting of Zn, Cd, Mn, and a mixture thereof, C comprises a polymer organic compound, a is higher than or equal to 0, b, c, d, e and f are higher than 0, f is equal to (2a+2b+6c+6d+3e)/2, the (a+b)/(c+d) ratio is 0.9 to 1.1, the a/b ratio is 0 to 1.5, the c/d ratio is 0.2 to 5, the (a+b+c+d)/e ratio is 0.6 to 5, and p is the weight percentage of C with respect to the total weight of the mixed oxide of formula (I), and is higher than 0% and lower than or equal to 40%, said mixed oxide of formula (I) comprising an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite, wherein said process comprises: 1) mixing at least one soluble source of W and at least one soluble source of Mo into a suitable volume of water, until obtaining a clear aqueous solution; 2) optionally, adding at least one source of at least one element Me to the solution obtained in 1; 3) adding at least one source of Ni to the mixture obtained in 2; 4) subjecting the mixture obtained in 3 to a first heat treatment at temperatures of 50° to 80° C., under stirring; 5) adding to the mixture obtained in 4, at least one soluble, hydrolysable or dispersible source of Al, and at least one polymer organic compound; 6) subjecting the mixture obtained in 5 to a second heat treatment at temperatures of 80° C. to 95° C., under stirring, obtaining a suspension; 7) subjecting the suspension obtained in 6 to drying, obtaining in such a way a solid phase; 8) calcining said solid phase obtained in 7, obtaining the mixed oxide of formula (I).

4. The process of claim 3, wherein the element Me is added in 2) and is Zn.

5. The process of claim 3, wherein the element Me is added in 2) and is Mn.

6. The process of claim 3, wherein 2) is omitted.

7. The process of claim 3, wherein the first heat of 4) is carried out for 10 minutes to 1 hour.

8. The process of claim 3, wherein as source of aluminum in 5), a dispersible alumina is used.

9. The process of claim 3, wherein the polymer organic compound added in 5) of said process is methylcellulose.

10. The process of claim 3, wherein in 5) a dispersion is added, which is separately prepared and comprising both said at least one soluble, hydrolysable or dispersible source of Al and said at least one polymer organic compound.

11. The process of claim 3, wherein the second heat treatment of 6) is carried out for 5 to 30 hours.

12. The process of claim 3, further comprising T) immediately after 7) wherein the dried solid phase obtained in 7) is subjected to shaping.

13. The process of claim 3, wherein the calcination in 8) is carried out under inert or air atmosphere, at temperatures of 200° C. to 450° C.

14. The process of claim 3, wherein the percentage “p” of said organic component C and possibly of the residue of said organic component C, in the composition of the mixed oxide obtained by said process, is 0.01% to 30%.

15. The process of claim 1, further comprising step 5′) adding an inorganic binder B, which is immediately after 5).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0041] FIG. 1 shows the .sup.27Al-MAS-NMR spectra of samples of mixed oxide of formula (I) (spectrum a) and of formula (I) bound with an Al-based inorganic binder B (spectrum b), prepared according to the process of the present invention and analyzed after calcination at a temperature comprised between 300 and 400° C.

[0042] FIG. 2a the XRD spectra of a mixed oxide of formula (I) wherein the metal Me is absent (the index “a” is equal to 0) are reported and FIG. 2b, the XRD spectra of a mixed oxide of formula (I) wherein the metal Me is present and it is Zn are reported. In both cases, the spectra were obtained on samples analyzed after drying (spectrum a), after calcination at a temperature comprised between 300 and 400° C. (spectrum b) and after calcination at 600° C. (spectrum c) corresponding to the mixed oxide.

[0043] FIG. 3a shows FT-IR spectra obtained ater drying (120° C.), after calcination at a temperature comprised between 300 and 400° C. (350° C.) and after complete calcination (600° C.) of a mixed oxide of formula (I) comprising the metal Me and wherein Me=Zn, obtained by the process according to the invention and FIG. 3b shows the FT-IR spectra of selected precursors of metals used in the preparation of the above-mentioned mixed oxide.

[0044] For the aims of the present description and the following claims, the definition of the numerical ranges always comprises the end-points, unless otherwise specified.

[0045] In the description of the embodiments of the present invention, the use of the terms “comprising” and “containing” means that the options described, for example relating to the steps of a method or a process or the components of a product or a device, are not necessarily exhaustive. However, it is important to note that an object of the present invention are also the embodiments wherein the term “comprising” referred to the options described, for example such options relating to the steps of a method or a process or the components of a product or a device, is to be interpreted as “consisting essentially of” or “consisting of”, even if not explicitly declared.

[0046] For the aims of the present description and the following claims, for the chemical elements and the belonging groups reference is to be made to the periodic table of elements reported in CRC Handbook of Chemistry and Physics (Ed. 58, 1977-1978) and using the CAS numbering. Particularly, for the aims of the present invention the expressions “Group VIB” and “metals of Group VIB” comprise chromium, molybdenum, tungsten, and mixtures thereof, in the elementary, ionic or compound form; the expressions “Group VIII” and “non-noble metals of Group VIII” comprise iron, cobalt, nickel, and mixtures thereof, in the elementary, ionic or compound form.

[0047] For the aims of the present invention, the term “bulk catalyst” means a non-supported catalyst, meaning in this way that the catalyst composition does not provide a preformed support on which metals are loaded by impregnation or deposition. Hereby the possibility that the compositions described and exemplified herein can comprise constituents different from those catalytically active, such as binders, promoters or additives, is not excluded.

[0048] For the aims of the present invention, the term “precursor of the crystalline phase isostructural to Wolframite” means a compound characterized in that it comprises an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite which, when subjected to calcination under oxidizing atmosphere, at temperatures equal to or higher than 600° C. for a period of time higher than or equal to 3 hours, develops in a crystalline phase isostructural to Wolframite which has a x ray diffraction “pattern” (“X-Ray Diffractometry”, XRD) comprising the signals reported in Table 1.

TABLE-US-00001 TABLE 1 No 2θ (°) Signal intensity 1 15.6 ± 0.1 Weak 2 19.3 ± 0.2 Strong 3 24.0 ± 0.3 Strong 4 24.9 ± 0.3 Strong 5 30.9 ± 0.5 Very strong 6 31.5 ± 0.5 Middle 7 36.7 ± 0.5 Strong 8 37.2 ± 0.5 Weak 9 39.2 ± 0.5 Middle 10 41.7 ± 0.6 Strong 11 46.5 ± 0.6 Weak 12 48.1 ± 0.6 Very weak 13 49.1 ± 0.6 Weak 14 52.3 ± 0.7 Middle 15 54.7 ± 0.7 Strong 16 58.8 ± 0.7 Very weak 17 62.6 ± 0.7 Middle 18 63.7 ± 0.7 Weak 19 66.0 ± 0.8 Strong 20 68.9 ± 0.8 Weak

[0049] The term “crystalline phase isostructural to Wolframite” means a phase having the same type of crystalline structure of natural Wolframite (mineral constituted by tungstate mixed of iron and manganese), for example a class of prismatic monoclinic symmetry, but different chemical composition, wherein then W, Fe, Mn can be partially or wholly substituted by different metals. The above-mentioned phase has a XRD pattern comprising the signals reported in Table 1.

[0050] For the aim of the present invention, the term “hydrotreatment” means a set of reactions wherein a hydrocarbon charge is contacted with hydrogen to modify the main chemical and physical properties. It is important to remember that in the refining sector, the hydrotreatment can have different names as a function of purpose (for example, hydrodesulphurization, hydrodenitrogenation, hydrodearomatization, hydrodemetalation, hydrodeoxygenation, hydrodecyclization, hydroisomerization, hydrocracking, hydrodewaxing, etcetera). The generic term of hydrorefining is usually used, said term can comprise the same above-mentioned hydrotreatment processes and distinguishing from it, in general, only for the less severe, but not always, conditions.

[0051] The hydrotreatment according to present invention can be carried out on a wide variety of petroleum- and petrochemical-derivatives, which comprise whole or reduced crude oils, residues or products of atmospheric distillation or under-vacuum, residues of processes of deasphalting with propane, for example “brick stock” fractions, Heavy and Light Cycle Oils, residues of the Fluid Catalytic Cracking (FCC) process, gas-oils from atmospheric distillation and under-vacuum, gas-oils from coker, light and heavy distillate, comprised “raw virgin” distillates, hydrocracking products, dewaxing products, petrolatum, products of Fischer-Tropsch process, refined products, naphthas, products from EST process and mixtures thereof.

[0052] As products from the EST process it is to be intended hydrocarbon fractions obtained, for example, from the processes described in U.S. Pat. Nos. 5,932,090, 7,255,795, WO2004/058922, WO2004/056946, WO2004/056947, WO2005/047425, WO2006/066911, WO2006/066857, WO2008/014947, WO2008/014948, WO2008/141830, WO2008/141831, WO2008/151792, WO2009/003633, WO2009/003634, WO20091/149923.

[0053] Preferably, the hydrotreatment relates to hydrocarbon cuts containing sulphur derivative contaminants and/or nitrogen derivative contaminants, in particular containing up to 40000 ppm of sulphur, possibly containing up to 2000 ppm of nitrogen. In said cuts up to 60% by weight of aromatic hydrocarbons can be present and up to 30% by weight of polycyclic aromatic hydrocarbons.

[0054] In a first aspect, it is an object of the present invention a process for obtaining a mixed oxide comprising Ni, Mo, W, Al, optionally at least one metal Me and an organic component C or a residue of said organic component C, having the following formula (I),

Me.sub.aNi.sub.bMo.sub.cW.sub.dAl.sub.cO.sub.f.pC  (I), [0055] wherein: [0056] Me is selected from the group consisting of Zn, Cd, Mn, and a mixture thereof, [0057] C comprises a polymer organic compound, [0058] a can be higher than or equal to 0, [0059] b, c, d, e and f are higher than 0, [0060] f is equal to (2a+2b+6c+6d+3e)/2, [0061] the (a+b)/(c+d) ratio is comprised between 0.9 and 1.1, [0062] the a/b ratio is higher than or equal to 0 and lower than or equal to 1.5, [0063] the c/d ratio is comprised between 0.2 and 5, [0064] the (a+b+c+d)/e ratio is comprised between 0.6 and 5, and [0065] p is the weight percentage of C with respect to the total weight of the mixed [0066] oxide of formula (I), and is higher than 0% and lower than or equal to 40%, said mixed oxide of formula (I) comprising an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite, wherein said process comprises the following steps: [0067] 1) mixing at least one soluble source of W and at least one soluble source of Mo into a suitable volume of water, until a clear aqueous solution is obtained, [0068] 2) optionally, adding at least one source of at least one element Me to the solution obtained in step 1; [0069] 3) adding at least one source of Ni to the mixture obtained in the previous step. [0070] 4) subjecting the mixture obtained in step 3 to a first heat treatment at temperatures comprised between 500 and 80° C., under stirring; [0071] 5) adding to the mixture obtained in step 4, at least one soluble, hydrolysable or dispersible source of Al, and at least one polymer organic compound; [0072] 6) subjecting the mixture obtained in the previous step to a second heat treatment at temperatures comprised between 80° C. and 95° C., under stirring, obtaining a suspension: [0073] 7) subjecting the suspension obtained in step 6 to drying, obtaining in such a way a solid phase; [0074] 8) calcining said solid phase obtained in the previous step, obtaining the mixed oxide of formula (I).

[0075] In a preferred aspect of the invention, b, c, d, and e are higher than 0.1.

[0076] In a preferred aspect of the invention, a is higher than 0 and more preferably a is higher than 0.1.

[0077] The process above described can be carried out sequentially from step 1 to step 8. However, in some preferred embodiments, at least one optional step can be omitted, or it is possible to add at least one additional step to said process, as better described in the following, without the object the invention to be modified.

[0078] The first step of the process consists of dissolving the tungsten source and the molybdenum source in an amount of water, preferably deionized or distilled water, at least sufficient to obtain a transparent solution.

[0079] Usable source of Mo and W are, for example, oxides, particularly acid oxides, the corresponding acids and ammonium salts thereof. Preferably, metatungstate is used as source of molybdenum ammonium and ammonium heptamolybdate is used as source of tungsten.

[0080] In the above-mentioned source of tungsten and molybdenum, the respective metals have a valence of 6.

[0081] The obtained mixture is maintained under stirring until a clear solution is obtained, indicating the total dissolution of Mo and W sources.

[0082] Preferably, step 1 of said process can be carried out at a temperature comprised between 25° C. and 50° C., in order to promote the above-mentioned dissolution.

[0083] According to optional step 2, a soluble or insoluble or partially soluble source of the element Me, preferably a soluble source, can be added to the obtained transparent solution.

[0084] Without wishing to be bound to any theory, the above mentioned element Me, when present, can have the function of promoting the formation of the pseudo-crystalline phase isostructural to Wolframite.

[0085] When the process comprises the addition of element Me, as already mentioned, said element can be selected from the group consisting of Zn, Cd and Mn, and a mixture thereof.

[0086] In a preferred aspect of the invention, the element Me optionally added to step 2 of said process can be Zn.

[0087] In a further preferred aspect of the invention, the element Me optionally added in step 2 can be Mn.

[0088] Usable sources of element Me can be, for example, the corresponding nitrates, acetates, carbonates, hydroxycarbonates.

[0089] When Me is Zn, zinc acetate or zinc hydroxycarbonate, preferably zinc acetate, can be used as sources of the element Me.

[0090] Preferably, when Me is Mn, manganese acetate can be used as a source of element Me.

[0091] In the above said source of the element Me, all the respective metals (Zn, Cd or Mn) have valence 2.

[0092] In a preferred aspect of the invention, the optional step 2 can be omitted. In this case, in the mixed oxide of formula (I) obtained at the end of the above-mentioned process, the element Me is not present, namely the “a” index of said element Me in the above-mentioned formula (I) is equal to 0.

[0093] Then, according to step 3 of the present process, a soluble, insoluble or partially soluble source, preferably a partially soluble source, of nickel is added.

[0094] Usable sources of Ni can be the correspondent nitrates, acetates, hydroxycarbonates, carbonates, acetylacetonates. Preferably, nickel hydroxycarbonate can be used.

[0095] Preferably, step 3 of said process can be carried out at a temperature comprised between 50° C. and 70° C., in order to promote the dissolution of said Ni source in the mixture obtained in the previous step.

[0096] The mixture obtained is subjected in step 4 to a first heat treatment, at temperatures comprised between 50° C. and 80° C., under stirring.

[0097] Preferably, said first heat treatment of step 4 can be carried out for a time comprised between 10 minutes and 1 hour, at temperatures comprised between 50° C. and 80′C, under stirring.

[0098] In a preferred aspect, said first heat treatment of step 4 of the present preparation process can be carried out at temperatures comprised between 55° C. and 70° C., maintaining the mixture constantly under stirring.

[0099] In a preferred aspect, the first heat treatment of step 4 of said processes can be carried out under constant stirring for a time comprised between 20 and 40 minutes.

[0100] In a particularly preferred aspect of the present invention, the first heat treatment of step 4 of said process can be carried out at a temperature comprised between 55 and 70° C. for a time comprised between 20 and 40 minutes, under constant stirring.

[0101] At the end of this heat treatment step, the process envisages that, in step 5, the at least one soluble source of aluminum, hydrolysable or dispersible, and at least one polymer organic compound, can be added to the mixture thus obtained.

[0102] As aluminum sources, for example, aluminum lactate, or dispersible alumina, or alumina monohydrate, or alumina trihydrate, or aluminum trialkoxides, wherein the alkyl is linear or branched and can contain from 2 to 5 carbon atoms, can be used and preferably a dispersible alumina is used.

[0103] Preferably, the dispersible alumina, added as aluminum source in step 5 of said process, can be a boehmite or pseudo-boehmite characterized by particles having an average diameter lower than 100 μm. Usable dispersible aluminas can be, for example, bohemites commercially available of the series Versal®, Pural®, Catapal®, Dequadis®, Disperal® and Dispal®.

[0104] Among the dispersible aluminum sources, water-dispersible aluminas or aluminas dispersible in aqueous solutions containing a monovalent acid, at room temperature, under stirring, can be particularly preferred: this aluminas are nanodimensional in the dispersed phase, characterized by particles sizes in dispersion comprised between 10 and 500 nm. Dispersible aluminas of this type which are advantageously usable are, for example, commercially available boehmites of the series Disperal P3® (Al.sub.2O.sub.3 68% by weight) and Dequadis HP®.

[0105] Preferably, the sources of hydrolysable aluminum which, starting from aluminum monomeric precursors, guarantee its good dispersion, can be trialkylaluminates wherein the alkyl group contains from 3 to 4 carbon atoms.

[0106] It is important to note that the 1-aluminas are not comprised among the aluminum source usable in this step.

[0107] In a preferred aspect of the invention, the source of Al can be added to step as dispersion previously prepared in the following manner: a soluble source of Al, hydrolysable or dispersible, in an amount comprised between 5 and 25% by weight, preferably between 8 and 18% by weight, is added to an aqueous solution containing between 0.2 and 2% by weight of acetic acid. The obtained dispersions is stirred for a time comprised between 1 and 48 hours, preferably between 3 e 24 hours, at a temperature comprised between 25 and 90° C., preferably between 30 and 70° C.

[0108] Then, in order to promote the homogeneity of the composition and improve the textural properties of the final mixed oxide, a polymer organic compound is added to the obtained dispersion after the addition of the Al source.

[0109] The above-mentioned polymer organic compound added in step 5 of said process preferably comprises one or more heteroatoms selected from N and O and can be selected, for example, from the group consisting of ammonium alginate, methylcellulose, propyl methylcellulose, ethylene glycol and propylene glycol copolymers, octylphenol ethoxylated, polioxyethylene cetyl ether.

[0110] In a preferred aspect, the polymer organic compound added to step 5 of said process is methylcellulose. In such a case, a commercially available methylcellulose can be used, such as, for example, methylcellulose Fluka® (viscosity of a suspension 2% in water=1200-1800 cP), methylcellulose Acros® (viscosity of a suspension 2% in water=15 cP), propyl methylcellulose Dow® Methocel® 311 (viscosity of a suspension 2% in water>1000 cP).

[0111] In a further preferred aspect of the present invention, the polymer organic compound added in step 5 of said process can be ammonium alginate.

[0112] In other preferred forms of the present invention, a polyethylenglycol-polypropylenglycol-polyethylenglycol block copolymer, (for example, the polymer commercially available as Pluronic® P123 with a viscosity at 60° C.=350 cP), or octylphenol ethoxylated (commercially available as Triton® X-305, with properties of non-ionic surfactant, characterized by a viscosity at 25° C.=470 cP), or polyoxyethylene cetyl ether (commercially available as Brij® 58, with properties of non-ionic surfactant, characterized by a relative viscosity (H.sub.2O=1) 5% in water at 25° C.=1.2-1.5), can be used as polymer organic compound, Said polymer organic compounds can be added in a percentage variable between 1% and 10% by weight with respect to the weight of metals present in the mixture.

[0113] In a preferred aspect, said polymer organic compound can be added in a percentage comprised between 1% and 5% by weight with respect to the weight of the metals.

[0114] Therefore it is apparent that the amount of polymer organic compound in the process of preparation of the catalyst according to the invention is particularly lowered: this allows that during the following mixed oxide calcination, smaller amounts of volatile organic compounds are produced, in particular nitrogenous compounds, so as to not necessarily require the treatment of emitted vapors into post-combustion chambers.

[0115] According to an alternative embodiment of the present invention, in step 5 the above-mentioned process, instead of separately adding at least one soluble, hydrolysable or dispersible source of Al and then at least one polymer organic compound, a dispersion, prepared separately and comprising both said at least one soluble, hydrolysable or dispersible source of Al and said at least one polymer organic compound, can be added.

[0116] In order to prepare the above-mentioned dispersion comprising both Al and the polymer organic compound, the procedure is the following: a soluble, hydrolysable or dispersible source of Al is added to an aqueous solution containing acetic acid and the obtained dispersion mixed with an aqueous suspension comprising a polymer organic compound and previously maintained under stirring for a period comprised between 20 minutes and 1 hour at a temperature comprised between 25 and 80° C.

[0117] Also in this case, the polymer organic compounds can be added in a percentage variable between 1% and 10% by weight with respect to the weight of metals present in the mixture.

[0118] In a preferred aspect, said polymer organic compound can be added in a percentage comprised between 1% and 5% by weight with respect to the weight of the metals.

[0119] After the addition of the polymer organic compound, the dispersion comprising both the soluble, hydrolysable or dispersible source of Al and the polymer organic compound, is stirred for a time comprised between 1 and 48 h, preferably between 3 and 24 h, and at a temperature comprised between 25 and 90° C., preferably between 30 and 70° C. before to be added to the metal-containing mixture obtained in step 3 of the process according to the invention.

[0120] Both by adding the Al source separately from the polymer organic compound, and by adding these two components together, as above described, the obtained mixture, comprising Mo, W, Ni, Al, the polymer organic compound, and optionally Me, is further subjected in subsequent step 6, to a second heat treatment at temperatures comprised between 80° C. and 95° C., under stirring.

[0121] Preferably, said second heat treatment is carried out at temperatures comprised between 80° C. and 95° C. for a time comprised between 5 and 30 hours, under stirring.

[0122] This second heat treatment allows to obtain an homogeneous suspension, wherein the metal components possibly deriving from non-soluble or partially soluble sources can interact and establish a close contact with each other. Preferably, the suspension obtained in step 6 can have a theoretical content of metal oxides comprised between 15 and 40% by weight, preferably between 18 and 30% by weight with respect to the total weight of the suspension.

[0123] In a preferred aspect of the invention, said second heat treatment can be carried out at temperatures comprised between 85° C. and 92° C.

[0124] In a preferred aspect of the invention, said second heat treatment can be carried out for a time comprised between 15 and 25 hours.

[0125] In a particularly preferred aspect of the invention, said second heat treatment of step 6 can be carried out at temperatures comprised between 85° C. and 92′C for a time comprised between 15 and 25 hours.

[0126] The suspension thus obtained is subjected to a step 7 of drying. The main function of the drying of step 7 is to remove the water present in the suspension, thus allowing to obtain a solid phase.

[0127] The drying of step 7 can be carried out by using any of the techniques known to one skilled in the art, for example, static oven, or by “belt drying” or “flash drying” or “spray drying” and preferably it is carried out by “spray drying”.

[0128] In a preferred aspect, the drying can be carried out at a temperature comprised between 100° C. and 250° C.

[0129] The time necessary to prevent a solid phase is related to the method used to carry out the drying operation of step 7. Identifying the more suitable time for each method use, in order to obtain the desired solid phase, is within the abilities of the skilled person.

[0130] It is important to note that step 6, in which the second heat treatment is carried out, is distinct from step 7 of drying, even if the two steps can be carried out possibly through the same principle, namely by heat administration for a suitable time, in view of the fact that, unlike step 6, from which it is possible to obtain a suspension, even extremely dense, in the drying step 7 is essential to obtain a solid phase substantially free of liquid phase.

[0131] In a preferred aspect of the invention, after drying, the obtained solid phase can be subjecting to shaping.

[0132] In this case, the process according to the present invention can comprise an additional step 7′ immediately subsequent to step 7, wherein the dried solid phase obtained in said step 7 is subjecting to shaping.

[0133] All the shaping techniques can be used for this purpose. The shaping can be carried out by tableting, extrusion, granulation, spherulization or atomization by spray-drying.

[0134] In order to facilitate the shaping operations, it is possible to add one or more organic additives to the mixed oxide in order to improve the rheology properties of the above-mentioned mixed oxide. These additives preferably can comprise: starch, cellulose, stearate, surfactant agents, or a mixture thereof.

[0135] The last step of the process provides the partial calcination of the mixed oxide prepared. The calcination of step 8 can be carried out under air or inert atmosphere, at temperatures higher than or equal to 200° C. and lower than or equal to 450° C. In a preferred aspect, the calcination can be carried out at temperatures comprised between 300° C. and 400° C.

[0136] The partial calcination can be carried out at a constant temperature or under a temperature gradient (or “programming”). The calcination time can vary preferably from a minimum of 3 hours up to 20 hours. Based on the calcination temperature and calcination time, the mixed oxide obtained can contain variable percentages, higher than 0 and lower than or equal to 40%, of the organic component C and/or of a residue of said organic component C.

[0137] For the aims of the present invention, the term “residue of the organic component C” means the set of the compounds, not better characterized, possibly present and deriving from said organic component C by thermal decomposition or degradation during the calcination process.

[0138] The above-mentioned organic component C can comprise, in addition to the polymer organic compound previously described, an organic portion deriving from the metal sources (for example acetate ion, acetylacetonate ion, lactate ion, alkoxide) and acetic acid, possibly used in the preparation process of the mixed oxide according to the invention.

[0139] The organic component C (and possibly the above-mentioned residue of the organic component C) can be quantitatively measured by thermogravimetry and differential thermal analysis (TG-DTA) on a sample of mixed oxide by using a Mettler thermobalance (mod. TG50). The test is carried out by subjecting the sample to a heating ramp of 10° C./min under air flux (200 cm.sup.3/min) from 30° C. to 600° C. The content of the organic component C (and possibly the above-mentioned residue of the organic component C), is expressed as percentage (percentage “p”) by weight with respect to the total weight of the mixed oxide, and it is calculated depending on the loss of weight of the sample analyzed through TG-DTA in the range 150-600° C.

[0140] In a preferred aspect, after calcination, the percentage “p” of said organic component C and possibly of the residue of said organic component C, in the composition of the mixed oxide obtainable by the process of the present invention, can be higher than or equal to 0.01% and lower than or equal to 30%, In a preferred aspect, “p” can be higher than or equal to 0.2% and lower than or equal to 10%.

[0141] In a preferred embodiment of the invention, the process according to the invention provides the introduction of the element Me, in step 2.

[0142] Therefore, according to a preferred embodiment of the present invention, the process for obtaining a mixed oxide comprising Ni, Mo, W, Al, at least one metal Me and an organic component C or a residue of said organic component C, having the following formula (I),

Me.sub.aNi.sub.bMo.sub.cW.sub.dAl.sub.cO.sub.f.pC  (I), [0143] wherein: [0144] Me is selected from the group consisting of Zn, Cd, Mn, and a mixture thereof, [0145] C comprises a polymer organic compound, [0146] a, b, c, d, e and f are higher than 0, [0147] f is equal to (2a+2b+6c+6d+3e)/2, [0148] the (a+b)/(c+d) ratio can be comprised between 0.9 and 1.1, [0149] the a/b ratio can be higher than or equal to 0 and lower than or equal to 1.5, [0150] the c/d ratio can be comprised between 0.2 and 5, [0151] the (a+b+c+d)/e ratio can be comprised between 0.6 and 5, and [0152] p is the weight percentage of C with respect to the total weight of the mixed oxide of formula (I), and can be higher than 0% and lower than or equal to 40%, [0153] said mixed oxide of formula (I) comprising an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite, comprises the following steps: [0154] 1) mixing at least one soluble source of W and at least one soluble source of Mo into a suitable volume of water, until obtaining a clear aqueous solution; [0155] 2) adding at least one source, preferably soluble, of at least one element Me to the solution obtained in step 1; [0156] 3) adding at least one source, preferably partially soluble, of Ni to the mixture obtained in the previous step; [0157] 4) subjecting the mixture obtained in step 3 to a first heat treatment at temperatures comprised between 50° and 80° C., under stirring; [0158] 5) adding to the mixture obtained in step 4, at least one soluble, hydrolysable or dispersible source of Al, and at least one polymer organic compound; [0159] 6) subjecting the mixture obtained in the previous step to a second heat treatment at temperatures comprised between 80° C. and 95° C., under stirring, obtaining a suspension; [0160] 7) subjecting the suspension obtained in step 6 to drying, obtaining in such a way a solid phase; [0161] 8) calcining said solid phase obtained in the previous step, obtaining the mixed oxide of formula (I).

[0162] In a preferred aspect, a, b, c, d and e can be higher than 0.1.

[0163] Preferably, the first heat treatment of step 4 can be carried out for a time comprised between 10 minutes and 1 hour, at temperatures comprised between 50° C. and 80° C., under stirring.

[0164] Preferably, the second heat treatment of step 6 can be carried out for a time comprised between 5 and 30 hours, at temperatures comprised between 80° C. and 95° C., under stirring.

[0165] On the contrary, according to an alternative embodiment, the process according to the invention can exclude the introduction of element Me in step 2.

[0166] In this case, the step 2 of the process can be omitted and the “a” index in formula (I) is equal to 0.

[0167] An advantage of the present process consists in that it does not involve separating and washing operations of the obtained solid phase. The absence of these steps allows the maintenance of the atomic ratios between the metals present in the mixtures reacting during the whole process in the final solid product: accordingly, it is not necessary the analytic control for determining the final composition of the mixed oxide metals, corresponding to the atomic ratios of the metals used during the process, even after the calcination.

[0168] Furthermore, in this way the production of waters contaminated with the mixed oxide metals is avoided. This aspect has particular industrial and environmental relevance as these metals are generally toxic and some of them are classified among the carcinogenic compounds.

[0169] In a further embodiment of the present invention, the above described process can be modified so as to provide the addition of at least one inorganic binder B.

[0170] The process for preparing the mixed oxides of formula (I) bound to at least one inorganic binder B comprises all the steps of the process already described and comprises one additional step 5′, which is immediately after step 5 of said process, namely after the addition of the polymer organic compound, or, in the case where this latter is added in mixture with the aluminum source, after the addition of said mixture to the mixture obtained in step 4, wherein an inorganic binder B is added.

[0171] The above-mentioned inorganic binder B can be constituted by a material conventionally used as inorganic binder for catalysts. Non-limiting examples of inorganic binder can comprise, for example, silica, alumina, silico-alumina, silica coated with alumina and alumina coated with silica, gibbsite, titania, zirconia, anionic and cationic clays, saponite, bentonite, kaolin, sepiolite or hydrotalcite, or mixtures thereof. Preferred binding material are silica, alumina, silico-alumina or mixtures thereof. In particular, γ-alumina can be used as source of alumina, possibly in the form of aqueous dispersion.

[0172] When the mixed oxide of the present invention is bound with at least one inorganic binder B wherein B contains Al, two forms structurally different of said metal are detectable in the above-mentioned mixed oxide, to which different functions are associated (component of the catalytic composition and function of inorganic binder, respectively).

[0173] The presence of two aluminum forms structurally different in the mixed oxide described above was confirmed by comparing through solid-state spectroscopy .sup.27Al MAS NMR, a mixed oxide of formula (I) and the corresponding mixed oxide bound to an Al-based inorganic binder B. An instrument Varian V-500, a pulse time of 0.2 μs (10° pulse) and a relaxing delay of 1 s were used for the test. The rotor of 4 mm containing the powder rotated at 14 kHz. The spectra were obtained at 130 MHz; the chemical shifts were referred to aluminum trichloride in solution (at 0 ppm). The .sup.27Al-MAS-NMR spectra of the samples of mixed oxide of formula (I) without inorganic binder (spectrum a) and bound to an Al-based inorganic binder B (spectrum b), prepared according to the process of the present invention and analyzed after the calcination at a temperature comprised between 300 and 400° C., are reported in FIG. 1. Disregarding the “spinning side bands” (indicated by the asterisks in FIG. 1), it can be noted the presence of two different signals with a chemical shift equal to 6±5 and 64±5 ppm attributed to Al atoms, in an octahedral [AlO] and tetrahedral coordination [AlO.sub.4], respectively. The relative abundance of the two species, expressed as mol %, was obtained through the process of signal deconvolution and calculation of the underlying area and is reported in Table 2.

[0174] As evident, the sample of mixed oxide of formula (I) has almost exclusively Al in an octahedral coordination, whereas the sample corresponding to the mixed oxide bound to the Al-based inorganic binder B, as well as the aluminum octahedral component, has a second Al component with an octahedral and tetrahedral coordination, compatible with the presence of γ-alumina as inorganic binder. The aluminum present as γ-alumina constitutes only a portion of the total aluminum present in the sample of mixed oxide bound to at least one inorganic binder B, according to a lower content of [AlO.sub.4] mol %, with respect to a sample of γ-alumina.

TABLE-US-00002 TABLE 2 [AlO.sub.6] [AlO.sub.4] Sample mol % mol % Reference Mixed oxide of 99 1 — formula (I) Mixed oxide of 81 19 — formula (I) bound to an Al-based inorganic binder B γ-alumina 70 30 M.-H. Lee, C.-F. Cheng, V. Heine and J. Klinowski. Chem. Phys. Len. 265, 673-676 (1997)

[0175] In a preferred aspect of the invention, also in the process of preparation of the mixed oxide of formula (I) bound to at least one inorganic binder B, a step of shaping after the drying of the obtained solid phase can be included.

[0176] Similarly to as described above, for this purpose the process according to the present invention can comprise a step 7′ immediately subsequent to step 7 of drying in which the dried solid phase obtained in said step 7 is subjected to shaping.

[0177] Also the mixed oxide of formula (I) formed in the presence of at least one inorganic binder B, comprises an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite.

[0178] The mixed oxide of formula (I) bound to at least one inorganic binder B of the present invention can be subjected to calcination, before the use, under air of inert atmosphere, at temperatures higher than 250° C. and lower than or equal to 450° C. and preferably can be subjected to calcination at temperatures comprised between 300° C. and 400° C.

[0179] The calcination can be carried out at constant temperature or under temperature gradient (or “programming”), The calcination time can vary from a minimum of 3 hours up to 20 hours. Based on the calcination temperature and calcination time, the calcinated mixed oxide can contain variable percentages, higher than 0 and lower than or equal to 40%, of the organic component C and/or of a residue of said organic component C.

[0180] It is a second object of the present invention a mixed oxide comprising Ni, Mo. W, Al, optionally at least one metal Me and an organic component C or a residue of said organic component C, having the following formula (I):

Me.sub.aNi.sub.bMo.sub.cW.sub.dAl.sub.cO.sub.f.pC  (I), [0181] wherein: [0182] Me is selected from the group consisting of Zn, Cd, Mn, and a mixture thereof, [0183] C comprises a polymer organic compound, [0184] a is higher than or equal to 0, [0185] b, c, d, e and f are higher than 0, [0186] f is equal to (2a+2b+6c+6d+3e)/2, [0187] the (a+b)/(c+d) ratio is comprised between 0.9 and 0.1, [0188] the a/b ratio is higher than or equal to 0 and lower than or equal to 1.5, [0189] the c/d ratio is comprised between 0.2 and 5, [0190] the (a+b+c+d)/e ratio is comprised between 0.6 and 5, and [0191] p is the weight percentage of C with respect to the total weight of the mixed oxide of formula (I) and is higher than or equal to 0% and lower than or equal to 40%, [0192] said mixed oxide comprising an amorphous phase and a pseudo-crystalline phase isostructural to Wolframite.

[0193] In a preferred aspect, a is higher than 0 and more preferably a is higher than 0.1.

[0194] In a preferred aspect, b, c, d and e are higher than 0.1.

[0195] In a preferred aspect of the invention, when a is higher than 0 the element Me can be Zn.

[0196] In a further aspect of the present invention, when a is higher than 0, the element Me can be Mn.

[0197] In a further aspect of the present invention, the (a+b)/(c+d) ratio can be comprised between 0.8 and 2. In a further preferred aspect said (a+b)/(c+d) ratio can be equal to 1.

[0198] In a preferred aspect the a/b ratio can be higher than or equal to 0 and lower than or equal to 1. In a particularly preferred aspect the a/b ratio can be comprised between 0.1 and 0.4.

[0199] Preferably, the c/d ratio can be comprised between 0.4 and 3. In a particularly preferred aspect the c/d ratio can be comprised between 1 and 2.5.

[0200] Preferably, p can be higher than or equal to 0.01% and lower than or equal to 30%. In a further preferred aspect, p can be higher than or equal to 0.2% and lower than or equal to 10%.

[0201] In a preferred aspect, the mixed oxide of formula (I) can be obtained through the process of the present invention described above.

[0202] In a preferred aspect, said mixed oxide can be bound to at least one inorganic binder B.

[0203] In a preferred aspect, said mixed oxide of formula (I) bound to at least one inorganic binder B can be obtained through the process of the present invention, in the embodiment which envisages an additional step 5′ wherein said inorganic binder B is added. As already mentioned previously, the above-mentioned step 5′ is set after step 5 of said process, namely after the addition of the polymer organic compound, or, in case the latter is added in mixture with the aluminum source, after the addition of said mixture.

[0204] The mixed oxides of formula (I) obtained by the process according to the present invention, were characterized, before and after the calcination, by X ray diffractometry of the powders, by means of a Philips mod. X'Pert diffractometer with vertical goniometer equipped with a pulse-counting electronic system, by using the Cu Kα radiation (wavelength λ=0.154 nm) applying methods known to one skilled in the art.

[0205] For example, in FIG. 2a the XRD spectra of a mixed oxide of formula (I) are reported, wherein the metal Me is absent (the “a” index is equal to 0) whereas in FIG. 2b the XRD spectra of a mixed oxide of formula (I) are reported, wherein the metal Me is present and it is Zn, in both cases, the spectra were obtained on samples analyzed after drying (spectrum a), after calcination at a temperature comprised between 304) and 400° C. (spectrum b) and after calcination at 600° C. (spectrum c) of the corresponding mixed oxide.

[0206] After the calcination at a temperature comprised between 300 and 400° C. (FIGS. 2a and 2b, spectrum b) the above-mentioned mixed oxides of formula (I) are characterized for the presence of an amorphous phase and of a pseudo-crystalline phase.

[0207] Through heat treatment at 600° C. the pseudo-crystalline phase evolves towards the formation of a crystalline phase isostructural to Wolframite. The pseudo-crystalline phase present in the samples after calcination at a temperature comprised between 300 and 400° C. is therefore a precursor of a crystalline phase isostructural to Wolframite. In the X ray diffraction spectrum of calcinated samples at 600° C. (FIGS. 2a and 2b, spectra c), the signals reported in Table 1 above are distinguished. In particular, the mixed oxide comprising metal Me (FIG. 2b) is further characterized by at least two additional signals in the range comprised between 25° and 28° of the 2θ angle (at 26.2°, of very weak intensity and at 26.6°, of weak intensity).

[0208] In FIGS. 2a and 2b, spectra a, the X ray diffraction spectra of the samples highlight signals attributable to the mixed ammonium salts present. Therefore, the calcination treatment promotes the formation of the mixed oxides of formula (I), characterized by a crystalline phase isostructural to Wolframite, which is well crystalized after treatment at 600° C.

[0209] It is important to note that in the mixed oxide of formula (I) comprising the Me metal, in the x-rays diffraction spectrum at 120° C. 350-400° C. and 600° C. (FIG. 2b) are always present at least three signals in the range comprised between 25° and 28° of the 2θ angle.

[0210] The mixed oxide of formula (I) obtained through the process of the present invention, was further characterized by Fourier Transformed Infrared Spectroscopy (FT-IR), with a spectrometer Perkin-Elmer mod. Spectrum BX, using tablets of powders diluted in KBr (2% by weight in KBr), by applying methods known to one skilled in the art.

[0211] The FT-IR spectra obtained after drying (120° C.), after calcination at a temperature comprised between 300 and 400° C. (350° C.) and after complete calcination (600° C.) of a mixed oxide of formula (I) comprising the metal Me and where Me=Zn, obtained through the process according to the invention, are reported in FIG. 3a.

[0212] By comparison, the FT-IR spectra of selected precursors of the metals used in the preparation of the above-mentioned mixed oxide are reported in FIG. 3b.

[0213] The main signals FT-IR present in the solid after drying are attributable to precursors of metals usable in the synthesis: in particular the signal at about 1400 cm.sup.−1 is typical of the precursors of Mo, W, Ni and the signal at about 1070 cm.sup.−1 is typical of the Al precursor (pseudo-boehmite).

[0214] In the calcinated materials this signals are no longer present, thus indicating a reaction at the solid state between the metal components associated to the formation of a mixed oxide. In particular, in FIG. 3a (600° C.) is no longer detectable the typical signal of alumina at about 1070 cm.sup.−1, thus indicating that it is not present as such, in mixture with a mixed oxide of Zn, Ni, Mo and W. In other words, in the mixed oxides of formula (I) obtained through the process according to the invention, the aluminum added as soluble, hydrolysable or dispersible source of aluminum has not the function of support or binder, and then of dilution, for the other metal components, but is in the composition of the mixed oxide in an equal manner with respect to the other metals. In particular, the mixed oxide of formula (I), independently from the fact that it comprises or it does not comprise the metal Me, produces a FT-IR spectrum wherein the signals at 805±10 cm.sup.−1, 605±10 cm.sup.−1 and 445±10 cm.sup.−1, which are typical of the Wolframite phase and whose definition increases with the calcination temperature, are recognized.

[0215] The surface area and the porosity of the mixed oxide of formula (I) obtained through the process of the present invention were determined from the isotherm of absorption/desorption of N.sub.2 at the temperature of −196° C., by using the Micrometrics TriStar® Surface Area and Porosity Analyzer, Before acquiring the isotherms, samples (about 0.3 g per test) were subjected to pre-treatment under-vacuum for 16 hours at 150° C.

[0216] The Specific Surface Area (SSA) was determined by the BET method (Brunauer-Emmett-Taller), known to the skilled person, carrying out the analysis in the range of relative pressure of P/P.sub.0 comprised between 0.05 and 0.3.

[0217] The above-mentioned mixed-oxide is characterized by having a specific Surface Area, determined after heat treatment at 350° C., higher than or equal to 80 m g. Preferably, the Specific Surface Area is comprised in the range 90-230 m.sup.2/g and more preferably it is comprised in the range 90-190 m.sup.2/g.

[0218] The mixed oxide of formula (I) obtained by the process according to the invention is mesoporous, namely, in accordance with the IUPAC terminology (Pure & Appl. Chem. Vol. 66, No. 8, pp. 1739-1758, 1994), is characterized by pore diameter comprised between 2 and 50 nm. Preferably the average pore diameter ranges from 4 to 10 nm.

[0219] The specific total volume of the pores was calculated by using the Gurvitsch method at 0.99 P/P.sub.0 and the pore distribution was determined by applying the BJH (Barret-Joyner-Hallender) method on the desorption curve. All the cited methods are known to one skilled in the art.

[0220] The mixed oxide of formula (I) obtained by the process of the present invention is characterized by a volume of the pores higher than or equal 0.15 mL/g. Preferably said volume of the pores is comprised between 0.15 and 0.35 ml/g.

[0221] The mixed oxide of formula (I), possibly bound to at least one inorganic binder B, obtained by the process of the present invention can be transformed in the corresponding sulphide, and said sulphide can be advantageously used as hydrotreatment catalyst.

[0222] Therefore, it is a further object of the present invention a metal sulphide catalyst obtained by sulphidation of the mixed oxide of formula (I), possibly bound to at least one inorganic binder B.

[0223] In a preferred aspect, the mixed oxide of formula (I) subjected to sulphidation in order to provide the above-mentioned metal sulphide catalyst, is obtained by the process of preparation of said mixed oxide of formula (I), according to the invention.

[0224] According to a different embodiment of the invention, the metal sulphidated catalyst can be obtained by sulphidation of the mixed oxide of formula (I) bound to at least one inorganic binder B.

[0225] In a preferred aspect, the mixed oxide of formula (I) bound to at least one inorganic binder B subjected to sulphidation to provide the above-mentioned metal sulphide catalyst, is obtained by the process of preparation of said mixed oxide of formula (I) bound to at least one inorganic binder B, according to the invention.

[0226] In order to obtained the corresponding sulphidated composition active as hydrotreatment catalyst, the mixed oxide sulphidation of the present invention can be carried out by any one of the techniques known to the skilled person, by using any sulphiding agent, as described, for example, by J. H. Gary e G. E. Handwerk in “Petroleum Refining—Technology and Economics” (2001, M. Dekker) p. 177.

[0227] The sulphidation can be carried out in situ, namely in the same reactor wherein the hydrotreatment will be subsequently carried out, or ex situ. The sulphidation process can be carried out under reducing atmosphere, for example constituted by H.sub.2S and H.sub.2, or with CS.sub.2 and H.sub.2, at high temperature, preferably with H.sub.2S and H.sub.2, at a temperature comprised between 300° C. and 500° C., for a period sufficient to sulphidate the starting mixed oxide. For example, the sulphidation can be carried out for a time comprised between 1 and 100 hours and preferably it is carried out for a time comprised between 15 and 50 hours.

[0228] Alternatively, the sulphidation of the mixed oxides can be carried out by using dimethyldisulphide (DMDS) dissolved in a hydrocarbon charge such as, for example, naphtha or gas-oil, at temperatures comprised between 300° C. and 500° C.

[0229] Finally, in a further preferred aspect, the sulphidation can be carried out contacting the mixed oxide of the present invention directly with the sulphur-rich hydrocarbon charge to be treated, preferably at temperatures comprised between 300° C. and 500° C.

[0230] As above-mentioned, the catalyst of the present invention obtained by the sulphidation of the mixed oxide of formula (I) or the mixed oxide of formula (I) bound to at least one inorganic binder B, is a catalyst which is very active and stable, and it provides particularly high and wide-spectrum catalytic performances in the hydrotreatment process, comprising, in addition to hydrodesulphurization and hydrodenitrogenation, also the hydrodearomatization and the reduction of the content of polycyclic aromatic hydrocarbons in the treated hydrocarbon mixtures.

[0231] Conversely, the above-mentioned catalyst shows a poor tendency to catalyze hydrocracking reactions.

[0232] Therefore, it is a further object of the present invention, a hydrotreating process of a feeding containing one or more hydrocarbons comprising contacting said feeding with hydrogen in the presence of a catalyst obtained by the sulphidation of the mixed oxide of formula (I) or the mixed oxide of formula (I) bound to at least one inorganic binder B.

[0233] Any feeding of hydrocarbon mixture containing impurities comprising sulphur and/or nitrogen can be treated with the catalyst of the present invention: for example, crude-oil distillates, crude oil residues, naphtha, etcetera, can be subjecting to the treatment, and preferably the hydrotreatment relates to hydrocarbon cuts containing contaminants comprising sulphur and/or contaminants comprising nitrogen.

[0234] Particularly, the metal sulphide catalyst of the present invention can be advantageously used for hydrotreating feedings comprising one or more hydrocarbons containing up to 4% w/w of S, up to 0.2% w/w of N and up to 50% w/w of polynuclear aromatic hydrocarbons.

[0235] Preferably the processing occurs at a temperature comprised between 100 and 450° C., more preferably between 30) and 370° C., at a pressure comprising between 5.0 and 10.0 MPa, more preferably between 5.0 and 7.0 MPa. The space velocity LHSV (Liquid Hour Space Velocity) can be comprised between 0.5 e 5 h.sup.−1, preferably between 0.8 and 2 h.sup.−1. The hydrogen amount can range between 100 and 800 times the hydrocarbon amounts, expressed as NI H.sub.2/l of hydrocarbon mixture.

[0236] In view of its capability to simultaneously carry out a high activity of hydrodesulphurization, hydrodenitrogenation, hydrodearomatization and reduction of the polynuclear aromatic compounds, the catalyst of the invention can be advantageously used also as hydrogenating component, associated to an acid components, in the hydrocracking process. Feeding suitable of hydrocracking, are, for example, heavy and extra-heavy crude oil, Vacuum Gas Oil (VGO), Vacuum Residues (VR).

[0237] In order to put into practice and better illustrate the present invention, some non-limiting examples, wherein the processes of preparation of mixed oxides of formula (I) which are precursors of the catalysts and the catalytic test, are reported below.

[0238] In all the examples, the composition molar formulas of the mixed oxide are normalized with respect to the sum (Ni moles+Zn moles)=1.00.

Example 1 According to the Invention (Preparation of a Mixed Oxide Having the Composition: Me.SUB.0.00.Ni.SUB.1.00.Mo.SUB.0.60.W.SUB.0.40.Al.SUB.1.04.O.SUB.5.56..6% C)

[0239] The preparation procedure of the mixed oxide involves the subsequent addition under suitable temperature conditions and stirring of solutions or dispersions containing the elements of the composition.

[0240] Firstly, 49.4 g of ammonium metatungstate hydrate (NH.sub.4)H.sub.2W.sub.12O.sub.40.xH.sub.2O were added to 154 g of water and the salt dissolution was promoted by using a rod-stirrer set at 180 rpm (peripheral speed=40 m/min). After about 15 minutes, 51.9 g of ammonium heptamolybdate (NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O were added to the solution and the mixture was heated at 50° C. under stirring in order to facilitate the dissolution of the molybdenum salt, 62.7 g of nickel hydroxycarbonate NiCO.sub.3.Ni(OH).sub.2.4H.sub.2O (58% by weight of NiO) were added after 30 minutes, bringing the mixture temperature to 70° C., and the same mixture was maintained at this temperature always under constant stirring for at least 30 minutes.

[0241] In the meantime, 36.7 g of Disperal® P3 Sasol (pseudoboehmite containing Al.sub.2O.sub.3 70% w/w) were mixed with 188.1 g of an aqueous solution of acetic acid 0.6% w/w. The mixture was maintained under stirring for about 2 hours, in order to obtain a homogeneous alumina dispersion.

[0242] Simultaneously, 4.7 g of methylcellulose Methocel® MC Fluka were added to 35.0 g of water at the temperature of 50° C. The mixture was maintained at 50° C. under stirring for about 10 minutes in order to obtain a homogeneous dispersion of the polymer organic compounds.

[0243] This latter was slowly added to the alumina dispersion, under stirring and maintaining the temperature at 50° C. until obtaining a homogeneous dispersion containing both alumina and the polymer organic compound.

[0244] Said homogeneous dispersion was added to the suspension containing Ni, Mo and W above described, maintained in turn at 70° C. under stirring. The addition is carried out very slowly and using a dropping funnel. At the end, the temperature of the mixture was brought to 90° C. and the obtained suspension was maintained at such temperature under stirring for about 18 hours. The pH of the suspension measured at the end of the above-mentioned heat treatment was equal to 5.6, and the content of Methocel® MC was equal to 3.1% by weight with respect to the theoretical content of mixed oxide.

[0245] At the end of this treatment, the dispersion thus obtained, which has a theoretical content of oxides equal to 26% by weight, was cooled and subjected to drying for about 20 minutes in a pre-heated oven at 200° C. Part of the obtained solid (50 g) was calcinated in static air according to the following programmed temperature: from room temperature at 200° C. in 30 minutes with a ramp of 6° C./min, isotherm at 200° C. for 10 minutes, heating up to 350° C. in 2 hours and 35 minutes with a ramp of about 1° C./min, isotherm at 350° C. for 5 hours.

[0246] The .sup.27Al MAS NMR spectrum is reported in FIG. 1 a, from which it can be calculated that 99 mol % of aluminum occupy an octahedral coordination.

[0247] A part of the sample calcinated at 350° C. was further calcinated at 600° C. for hours. The XRD spectra of the samples subjected to several heat treatments are reported in FIG. 2 a.

[0248] The remaining part of the sample dried at 200° C. was then placed into a mechanical mixer and mixed at a temperature of about 50° C. for about 2 hours, until obtaining an homogeneous paste with a suitable consistency to be extruded. The extrudate was aged at room temperature for 15 hours, then calcinated with the ramp described above.

[0249] The final mixed oxide extruded has the following molar composition: Ni.sub.1.00Mo.sub.0.60W.sub.0.40Al.sub.1.04O.sub.5.56. The mixed oxide contains 6.0% by weight of organic component residue with respect to the total weight of the solid.

[0250] The Specific Surface Area (SSA) is 142 m.sup.2/g, the total volume of the pores (Vp) is 0.18 cm.sup.3/g, the average pore size is 4.0 nm calculated from the desorption isotherm.

Example 2 According to the Invention (Preparation of a Mixed Oxide Having the Composition: Me.SUB.0.00.Ni.SUB.1.00.Mo.SUB.0.50.Al.SUB.1.04.O.SUB.5.56..6.3% C)

[0251] The procedure of example 1 was repeated by modifying the amounts of ammonium metatungstate hydrate (NH.sub.4).sub.6H.sub.2W.sub.12O.sub.40.xH.sub.2O (61.7 g) and of ammonium heptamolybdate (NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O (43.2 g).

[0252] The obtained mixed oxide has the following molar composition: Ni.sub.1.00Mo.sub.0.50W.sub.0.50Al.sub.1.04O.sub.5.56. The mixed oxide contains 6.3% by weight of organic component residue with respect to the total weight of the solid. The Specific Surface Area (SSA) is 149 m.sup.2/g, the total volume of the pores (Vp) is 0.19 cm.sup.3/g, the average pore diameter is 4.4 nm calculated from the desorption isotherm.

Example 3 According to the Invention (Preparation of a Mixed Oxide Having the Composition: Me.SUB.0.50.Ni.SUB.0.50.Mo.SUB.0.50.Al.SUB.1.02.O.SUB.5.53..13.1% C, Wherein Me=Zn)

[0253] 61.7 g of ammonium metatungstate hydrate (NH.sub.4).sub.6H.sub.2W.sub.12O.sub.40.xH.sub.2O were added to 154 g of water and the salt dissolution was promoted by using a rod-stirrer set at 180 rpm (peripheral speed=40 m/min). After about 15 minutes, 43.2 g of ammonium heptamolybdate (NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O were added to the solution and the mixture was heated at 50° C. under stirring in order to facilitate the dissolution of the molybdenum salt, 53.9 g of Zn acetate Zn(CH.sub.3COO).sub.2.2H.sub.2O were added after 30 minutes, then the mixture was maintained at 50° C. and under stirring for other 30 minutes. Finally, 31.7 g of nickel hydroxycarbonate NiCO.sub.3.Ni(OH).sub.2.4H.sub.2O (58% by weight of NiO) were added, the mixture temperature was brought to 70° C., and the same mixture was maintained at this temperature always under constant stirring for at least 30 minutes.

[0254] In the meantime, 36.7 g of Disperal® P3 Sasol (pseudoboehmite containing Al.sub.2O.sub.3 70% w/w) were mixed with 188.1 g of an aqueous solution of acetic acid 0.6% w/w. The mixture was maintained under stirring for about 2 hours, in order to obtain a homogeneous alumina dispersion.

[0255] Simultaneously, 4.2 g of methylcellulose Methocel® MC Fluka were added to 35.0 g of water at the temperature of 50° C. The mixture was maintained at 50° C. under stirring for about 10 minutes in order to obtain a homogeneous dispersion of the polymer organic compound.

[0256] This latter was slowly added to the alumina dispersion, under stirring and maintaining the temperature at 50° C. until obtaining a homogeneous dispersion containing both alumina and the polymer organic compound.

[0257] Said homogeneous dispersion was added to the suspension containing Zn, Ni, Mo and W above described, maintained in turn at 70° C. under stirring. The addition is carried out very slowly and using a dropping funnel. At the end, the temperature of the mixture was brought to 90° C. and the obtained slurry was maintained at such temperature under stirring for about 18 hours. The pH of the suspension measured at the end of the above-mentioned heat treatment was equal to 5.6, and the content of Methocel® MC was equal to 3.1% by weight with respect to the theoretical content of mixed oxide.

[0258] At the end of this treatment, the dispersion thus obtained, which has a theoretical content of oxides equal to 22% by weight, with respect to the total weight of the dispersion, was cooled and subjected to drying for about 20 minutes in a pre-heated oven at 200° C.

[0259] The recovered solid phase was then calcinated in static air according to the following temperature program: from room temperature at 200° C. in 30 minutes with a ramp of 6° C./min, isotherm at 200° C. for 10 minutes, heating up to 350° C. in 2 hours and 35 minutes with a ramp of about 1° C./min, isotherm at 350° C. for 5 hours.

[0260] The final mixed oxide has the following molar composition: Zn.sub.0.50Ni.sub.0.50Mo.sub.0.50W.sub.0.50Al.sub.1.02O.sub.5.53. The mixed oxide contains 13.1% by weight of organic component residue with respect to the total weight of the solid.

[0261] The Specific Surface Area (SSA) is 142 m.sup.2/g, the total volume of the pores (Vp) is 0.21 cm.sup.3/g, the average pore size is 9 nm calculated from the desorption isotherm.

Example 4 According to the Invention (Preparation of a Mixed Oxide Having the Composition: Me.SUB.0.25.Ni.SUB.0.75.Mo.SUB.0.60.W.SUB.0.40.Al.SUB.3.03.O.SUB.5.55..14.9% C. Wherein Me=Zn)

[0262] 49.4 g of ammonium metatungstate hydrate (NH.sub.4).sub.6H.sub.2W.sub.12O.sub.40.xH.sub.2O were added to 154 g of water and the salt dissolution was promoted by using a rod-stirrer set at 180 rpm (peripheral speed=40 m/min). After about 15 minutes, 51.9 g of ammonium heptamolybdate (NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O were added to the solution and the mixture was heated at 50° C. under stirring in order to facilitate the dissolution of the molybdenum salts, 27.2 g of Zn acetate Zn(CH.sub.3COO).sub.2.2H.sub.2O were added after 30 minutes, then the mixture was maintained at 50° C. and under stirring for other 30 minutes. Finally, 47.0 g of nickel hydroxycarbonate NiCO.sub.3Ni(OH).sub.2.4H.sub.2O (58% by weight of NiO) were added, the mixture temperature was brought to 70° C., and the mixture was maintained to this temperature always under constant stirring for at least 30 minutes.

[0263] In the meantime, 36.7 g of Disperal® P3 Sasol (pseudoboehmite containing Al.sub.2O.sub.3 70% w/w) were mixed with 188.1 g of an aqueous solution of acetic acid 0.6% w/w. The mixture was maintained under stirring for about 2 hours, in order to obtain a homogeneous alumina dispersion.

[0264] Simultaneously, 4.4 g of methylcellulose Methocel® MC Fluka were added to 35.0 g of water at the temperature of 50° C. The mixture was maintained at 50° C. under stirring for about 10 minutes in order to obtain a homogeneous dispersion of the polymer organic compounds.

[0265] This latter was slowly added to the alumina dispersion, under stirring and maintaining the temperature at 50-C until obtaining a homogeneous dispersion containing both alumina and the polymer organic compound.

[0266] Said homogeneous dispersion was added to the suspension containing Zn, Ni, Mo and W above described, maintained in turn at 70° C. under stirring. The addition is carried out very slowly and using a dropping funnel. At the end, the temperature of the mixture was brought to 90° C. and the obtained slurry was maintained at such temperature under stirring for about 18 hours. The pH of the suspension measured at the end of the above-mentioned heat treatment was equal to 5.6, and the content of Methocel® MC was equal to 3.1% by weight with respect to the theoretical content of mixed oxide.

[0267] At the end of this treatment, the dispersion thus obtained, which has a theoretical content of oxides equal to 24% by weight, was cooled and subjected to drying for about 20 minutes in a pre-heated oven at 200° C.

[0268] The recovered solid phase was then calcinated in static air according to the following temperature program: from room temperature at 200° C. in 30 minutes with a ramp of 6° C./min, isotherm at 200° C. for 10 minutes, heating up to 350° C. in 2 hours and 35 minutes with a ramp of about 1° C./min, isotherm at 350° C. for 5 hours.

[0269] The final mixed oxide has the following molar composition: Me.sub.0.25Ni.sub.0.75Mo.sub.0.60W.sub.0.40Al.sub.1.03O.sub.5.55. The mixed oxide contains 14.9% by weight of organic component residue with respect to the total weight of the solid.

[0270] The Specific Surface Area (SSA) is 175 m.sup.2/g, the total volume of the pores (Vp) is 0.21 cm.sup.3/g, the average pore size is 4.1 nm calculated from the desorption isotherm.

[0271] A part of the sample was further calcinated at 600° C. for 5 hours. The XRD spectra of the samples subjected to several heat treatments are reported in FIG. 2 b. From the X-rays diffraction spectra at 120° C., 350-400° C. and 600° C. it was observed that at least three signals are always present in the range comprised between 25° and 280 of the 20 angle.

[0272] The FT-IR spectra of the samples subjected to several heat treatments are reported in FIG. 3 a.

Example 5 According to the Invention (Preparation of a Mixed Oxide Having the Composition: Me.SUB.0.25.Ni.SUB.0.75.Mo.SUB.0.60.W.SUB.0.40.Al.SUB.1.03.O.SUB.5.55..13.8% C −10% γ-Al.SUB.2.O.SUB.3., Wherein Me=Zn and Bound to 10% of Inorganic Binder 8)

[0273] This example discloses the preparation of a mixed oxide containing Zn and bound to an inorganic binder B, wherein the polymer organic compound used is Methocel® MC.

[0274] The process followed is identical to that described in previous example 4, with the difference that 58.0 g of dispersible γ-alumina (AERODISP® W925, γ-Al.sub.2O.sub.3 25% w/w) were added to the mixture before the final heat treatment of 18 hours.

[0275] The final mixed oxide has the following molar composition: Zn.sub.0.25Ni.sub.0.75Mo.sub.0.6W.sub.0.4Al.sub.1O.sub.5.5.10% γ-Al.sub.2O.sub.3. The mixed oxide contains 13.8% by weight of organic component residue with respect to the total weight of the solid.

[0276] The Specific Surface Area (SSA) is 145 m.sup.2/g, the total volume of the pores is 0.23 cm.sup.3/g, the average pore size is 4.0 am calculated from the desorption isotherm.

[0277] The X-ray diffraction spectrum of the obtained mixed oxide allows to detect at least three signals in the range of the 20 angle comprised between 21° and 28°.

[0278] The .sup.27Al-MAS-NMR spectrum is reported in FIG. 1 b, from which it was calculated that 81 mol % of aluminum occupy an octahedral coordination.

Example 6 Comparative (Preparation of a Mixed Oxide Having the Composition: Ni.SUB.1.0.Mn.SUB.0.5.W.SUB.0.54.Al.SUB.0.57.O.SUB.4.98.. 2.0% C, not According to the Invention)

[0279] 7.56 g of octylamine were dissolved in 40 g of absolute ethanol. A solution containing 14.89 g of nickel hexahydrate nitrate Ni(NO.sub.3).sub.2.6H.sub.2O, 4.52 g of ammonium heptamolybdate (NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O and 6.98 g of ammonium metatungstate hydrate (NH.sub.4).sub.6H.sub.2W.sub.12O.sub.40.xH.sub.2O dissolved in 50 ml of an aqueous sol containing 14.90 g of an aqueous dispersion of boehmite (Disperal® P2 by Sasol™) % by weight was added under stirring to this solution. The octylamine/(Ni+Mo+W) molar ratio is equal to 0.6. A light green gel, which was left under stirring for 3 hours, heating at 70° C., was formed. It was left to stand for 48 hour. The gel obtained did not have supernatant and it was dried into a oven at 90° C. for 48 hours. The dried material was subjected to heat treatment at 400° C. for hours in air.

[0280] The solid had the following molar composition Ni.sub.1.06Mo.sub.0.50W.sub.0.54Al.sub.0.57O.sub.4.98. The mixed oxide contains 2.0% by weight of organic component residue with respect to the total weight of the solid.

[0281] The specific surface area is 151 W/g, the total volume of the pores 0.381 cm.sup.3/g, the average diameter of the pores 6.3 nm, calculated from the desorption isotherm.

Example 7 (Catalytic Test)

[0282] The mixed oxides prepared according to the examples 1,2,4,5,6 were used in experiments wherein their effectiveness as hydrotreatment catalysts was verified.

[0283] In each experiment, 20 cm.sup.3 of mixed oxide, preventively pressed, granulated and sieved (10-16 meshes), were diluted with 20 cm of inert material (carborundum) and loaded into a fixed-bed reactor of volume equal to 40 ml. Then, the mixed oxide was treated with a sulphiding mixture, consisting of “Straight Run Gasoil” added with dimethyldisulphide (DMDS), so as to have a concentration of S equal to 2.5% by weight with respect to the total weight of the sulphide mixture. The used sulphidation conditions were:

[0284] LHVS=3 h.sup.−1

[0285] P=3.0 MPa

[0286] T=340° C.

[0287] H.sub.2/sulphide mixture=200 NL/L

[0288] Sulphidation time=26 h

[0289] To the sulphidation phase, in which the mixed oxide acquires the catalytic properties, a stabilization phase followed at T 330° C. for 60-100 h. maintaining the catalytic bed into contact with the “Straight Run” gas-oil.

[0290] The hydrotreatment reaction was carried out by feeding a mixture consisting of “Straight Run” gas-oil and “Visbreaking” in proportion 75:25 (w/w) and therefore characterized by high amounts of sulphur (2% w/w) and polynuclear aromatic hydrocarbons (17% w/w).

[0291] The reaction conditions were as follows:

[0292] P (H.sub.2)=4.9 MPa

[0293] H.sub.2/feed ratio=230 NL/L

[0294] LHSV=0.8 h.sup.−1

[0295] Reaction temperature=340° C.

[0296] The activity of each catalyst was assessed in percentage with respect to the catalyst activity of the comparative example 6 (set to 100%).

[0297] Data are reported in the following Table 4.

TABLE-US-00003 TABLE 4 Catalyst Composition HDS HDN HDA Example 1 Ni.sub.3.00Mo.sub.0.50W.sub.0.40Al.sub.3.04O.sub.5.36•6.0% C 100.1 100.1 253.8 Example 2 Ni.sub.1.00Mo.sub.0.50W.sub.0.50Al.sub.1.04O.sub.5.36•6.3% C 100.3 100.3 341.8 Example 4 Zn.sub.0.25Ni.sub.0.75Mo.sub.0.60W.sub.0.40Al.sub.1.03O.sub.5.56• 100.3 100.4 303.3 14.9% C Example 5 Zn.sub.0.25Ni.sub.0.75Mo.sub.0.60W.sub.0.40Al.sub.3.03O.sub.5.55• 100.1 100.3 224.2 13.8% C•10% γ-Al.sub.2O.sub.3 Example 6 Ni.sub.1.0Mo.sub.0.5W.sub.0.54Al.sub.0.57O.sub.4.98•2.0% C 100.0 100.0 100.0 comparative

[0298] Besides comparable performances of hydrodesulphurization (HDS) and hydrodenitrogenation (HDN), all the samples showed a significant increase of conversion in the hydrodearomatization (HDA).

[0299] It is important to note that also the catalyst of example 5, characterized by a lower content of metals, as it contains 10% by weight of inorganic binder B, is more active, mainly for the aims of the hydrodearomatization reaction, with respect to the catalyst of the comparative example.