Ammonia-free synthesis for Al or Si based multimetallic materials

Abstract

A highly active mixed transition metal oxide material has been developed. The material may be sulfided to generate metal sulfides which are used as a catalyst in a conversion process such as hydroprocessing. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

Claims

1. A mixed transition metal oxide material having the formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r where: M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4); M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10); M.sub.III is a metal selected from Group VIB (IUPAC Group 6); M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14); [R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms and R1, R2, R3 and R4 can be the same or different from each other; wherein m/(m+n)≥0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0, wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0 and wherein the material is further characterized by an X-ray diffraction pattern, with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si: TABLE-US-00015 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s TABLE-US-00016 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s wherein the listed peaks have a full width at half maximum greater than 0.75°.

2. The mixed transition metal oxide material of claim 1 wherein M.sub.I is Zr, Mn, Cu, Zn, or any mixture thereof.

3. The mixed transition metal oxide material of claim 1 wherein M.sub.II is Fe, Co, Ni, or any mixture thereof.

4. The mixed transition metal oxide material of claim 1 wherein M.sub.III is Cr, Mo, or W.

5. The mixed transition metal oxide material of claim 1 wherein the mixed transition metal oxide material is sulfided.

6. A method of making a mixed transition metal oxide material having the formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r where: M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4); M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10); M.sub.III is a metal selected from Group VIB (IUPAC Group 6); M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14); and [R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms and R1, R2, R3 and R4 can be the same or different from each other; wherein m/(m+n)≥0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0, wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0 wherein material is further characterized by an X-ray diffraction pattern, with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si: TABLE-US-00017 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s TABLE-US-00018 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s wherein the listed peaks have a full width at half maximum greater than 0.75° the method comprising: a) adding sources of M.sub.I, M.sub.II, M.sub.III, and M.sub.IV, to at least one short-chain alkyl quaternary ammonium hydroxide compound having the formula [R1 R2 R3 R4-N]OH, where R1, R2, R3 and R4 are alkyl radicals having 1 to 6 carbon atoms, and R1, R2, R3 and R4 can be the same or different to form a reaction mixture wherein the reaction mixture does not contain additional NH.sub.3.H.sub.2O or other basic solutions; (b) reacting the reaction mixture at a temperature from about 25° C. to about 200° C. for a period of time from about 30 minutes to 200 hours to generate the mixed transition metal oxide material; and (c) recovering the mixed transition metal oxide material.

7. The method of claim 6 wherein the reaction mixture is a slurry.

8. The method of claim 6 further comprising adding a binder to the reaction mixture or to the recovered mixed transition metal oxide material.

9. The method of claim 8 wherein the binder is selected from aluminas, silicas, alumina-silicas, titanias, zirconias, natural clays, synthetic clays, and mixtures thereof.

10. The method of claim 6 further comprising sulfiding at least a portion of the recovered mixed transition metal oxide material.

11. The method of claim 6 wherein the reacting is conducted under atmospheric pressure or autogenous pressure.

12. The method of claim 6 wherein the recovering is by decantation, filtration, or centrifugation.

13. The method of claim 6 further comprising continuous or intermittent mixing during the reacting, during the adding or both during the reacting and during the adding.

14. The method of claim 6 wherein the temperature is varied during the reacting.

15. A conversion process comprising contacting a material with a sulfiding agent to convert at least a portion of the material to metal sulfides and contacting the metal sulfides with a feed at conversion conditions to generate at least one product, wherein the material comprises a mixed transition metal oxide material having the formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r where: M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4); M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10); M.sub.III is a metal selected from Group VIB (IUPAC Group 6); M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14); and [R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms and R1, R2, R3 and R4 can be the same or different from each other; wherein m/(m+n)≥0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0, wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0 and wherein the material is further characterized by an X-ray diffraction pattern, with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si: TABLE-US-00019 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s TABLE-US-00020 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s wherein the listed peaks have a full width at half maximum greater than 0.75°.

16. The process of claim 15 wherein the conversion process is hydroprocessing.

17. The process of claim 16 wherein the conversion process is selected from hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

18. The process of claim 15 wherein the mixed transition metal oxide material is present in a mixture with at least one binder and wherein the mixture comprises up to about 80 wt % binder.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an XRD pattern of the material of example 1.

(2) FIG. 2 is an XRD pattern of the material of example 2.

(3) FIG. 3 is an XRD pattern of the material of example 3.

(4) FIG. 4 is an XRD pattern of the material of example 4.

(5) FIG. 5 is an XRD pattern of the material of example 5.

(6) FIG. 6 is an XRD pattern of the material of example 6.

(7) FIG. 7 is an XRD pattern of the material of example 7.

DETAILED DESCRIPTION OF THE INVENTION

(8) The present invention relates to a novel mixed transition metal oxide material, a process for preparing the material, and a process using the material. The material has an empirical formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r
where: M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4); M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10); M.sub.III is a metal selected from Group VIB (IUPAC Group 6); M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14); [R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, and R1, R2, R3 and R4 can be the same or different from each other. NH.sub.4 is an ammonium cation with one positive charge. OH and O are hydroxide anion and oxygen anion with one or two negative charges, respectively. a, b, c, and d are the valence states of M.sub.I, M.sub.II, M.sub.III, and M.sub.IV; x, y, m, n, o, p, q, and r are the mole ratio of [R1 R2 R3 R4-N] cation, NH.sub.4 cation, M.sub.I, M.sub.II, M.sub.III, M.sub.IV, O, and OH anion, wherein m/(m+n)≥0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0, wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0

(9) The material is further characterized by an X-ray diffraction pattern, which is essentially amorphous with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si:

(10) TABLE-US-00007 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s

(11) TABLE-US-00008 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s
wherein all the said peaks have a full width at half maximum greater than 0.75°.

(12) Although M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4), in one embodiment, M.sub.I may be selected from Zr, Mn, Cu, Zn, and any mixture thereof. Although M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10), in one embodiment M.sub.II may be selected from Fe, Co, Ni, and any mixture thereof. Although M.sub.III is a metal selected from Group VIB (IUPAC Group 6) in one embodiment, M.sub.III is selected from Cr, Mo, and W. Although M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) and Group IVA (IUPAC Group 14), in one embodiment, M.sub.IV is selected from Al and Si.

(13) The novel mixed transition metal oxide material can be prepared by co-precipitation by adding sources of the transition metals with one or more alkyl quaternary ammonium hydroxide compounds without using NH.sub.3.H.sub.2O or other basic solution. A protic solvent may be used as well. The term “metal” as used herein is meant to refer to the element and not meant to necessarily indicate a metallic form.

(14) Sources of M.sub.I include, but are not limited to, the respective halide, sulfide, acetate, nitrate, carbonate, sulfate, oxalate, thiols, hydroxide salts, and oxides of M.sub.I. Specific examples of sources of M.sub.I include, but are not limited to, manganese nitrate, manganese chloride, manganese bromide, manganese sulfate, manganese carbonate, manganese sulfide, manganese hydroxide, manganese oxide, zirconium nitrate, zirconium oxychloride, zirconium bromide, zirconium sulfate, zirconium basic carbonate, zirconium hydroxide, zirconium oxide, copper nitrate, copper chloride, copper bromide, copper sulfate, copper carbonate, copper acetate, copper oxalate, copper sulfide, copper hydroxide, copper oxide, zinc nitrate, zinc chloride, iron bromide, zinc sulfate, zinc carbonate, zinc acetate, zinc oxalate, zinc sulfide, zinc hydroxide, zinc oxide, and any mixture thereof.

(15) Sources of M.sub.II include, but are not limited to, the respective halide, sulfide, acetate, nitrate, carbonate, sulfate, oxalate, thiols, hydroxide salts, and oxides of M.sub.II. Specific examples of sources of M.sub.II include, but are not limited to, nickel chloride, nickel bromide, nickel nitrate, nickel acetate, nickel carbonate, nickel hydroxide, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt hydroxide, cobalt sulfide, nickel chloride, cobalt oxide, nickel bromide, nickel nitrate, nickel acetate, nickel carbonate, nickel hydroxide, nickel sulfide, nickel oxide, iron acetate, iron oxalate, iron nitrate, iron chloride, iron bromide, iron sulfate, iron carbonate, iron acetate, iron oxalate, iron sulfide, iron oxide, and any mixture thereof.

(16) Sources of M.sub.III include, but are not limited to, the respective oxides of M.sub.III, sulfides of M.sub.III, halides of M.sub.III, molybdates, tungstates, thiolmolybdates, and thioltungstates. Specific examples of sources of M.sub.III include, but are not limited to, molybdenum trioxide, ammonium dimolybdate, ammonium thiomolybdate, ammonium heptamolybdate, sodium dimolybdate, sodium thiomolybdate, sodium heptamolybdate, potassium dimolybdate, potassium thiomolybdate, potassium heptamolybdate, molybdenum sulfide, tungsten trioxide, tungstic acid, tungsten oxytetrachloride, tungsten hexachloride, hydrogen tungstate, ammonium ditungstate, sodium ditungstate, ammonium metatungstate, ammonium paratungstate, sodium metatungstate, sodium paratungstate, and any mixture thereof.

(17) Sources of M.sub.IV include, but are not limited to, aluminum chloride, aluminum bromide, aluminum fluoride, aluminum nitrate, ammonium aluminum sulfate, aluminum tri-sec-butoxide, aluminum tert-butoxide, aluminum isopropoxide, aluminum ethoxide, aluminum acetylacetonate, sodium silicate, tetra-alkyl orthosilicate, silica hydrogel, colloidal silica, silica hydroxide, fumed silica, silicic acid, and any mixtures thereof.

(18) The short-chain alkyl quaternary ammonium hydroxide compound is selected from compounds having the formula [R1 R2 R3 R4-N]OH, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, and R1, R2, R3 and R4 can be the same or different from each other. Specific examples of short-chain alkyl quaternary ammonium hydroxide compounds include, but are not limited to, tetra methyl ammonium hydroxide, tetra ethyl ammonium hydroxide, tetra propyl ammonium hydroxide, tetra butyl ammonium hydroxide, tetra pentyl ammonium hydroxide, tri-butyl methyl ammonium hydroxide, tri-propyl methyl ammonium hydroxide, tri-ethyl methyl ammonium hydroxide, di-propyl di-methyl ammonium hydroxide, butyl tri-methyl ammonium hydroxide, and any mixture thereof.

(19) The material of this invention can be prepared by co-precipitation by adding the sources of transition metals to at least one alkyl quaternary ammonium hydroxide compound. The resulting reaction mixture may be a slurry. In one embodiment, the sources of the transition metals are added to the at least one quaternary ammonium hydroxide compound, and in this embodiment, mixing is optional. Optionally, a protic solvent may be added as well Suitable protic solvents include water and alcohols such as ethanol, isopropanol, butanol, and glycol. In other embodiment, the reaction mixture may be formed by adding the components of the reaction mixture in any order and in any combination and as a variety of solutions. In one embodiment, the sources of M.sub.I, M.sub.II, M.sub.III, and M.sub.IV may be in one or more solutions prior to forming the reaction mixture. In one embodiment, sources or solutions of M.sub.I, M.sub.II, M.sub.III, and M.sub.IV may be mixed with protic solvent, an alkyl quaternary ammonium hydroxide solution, or any of the above prior to combination to form the reaction mixture. In another embodiment, the prepared M.sub.I, M.sub.II, M.sub.III, and M.sub.IV solutions can be added into protic solution and an alkyl quaternary ammonium hydroxide solution added to the protic solution to form the reaction mixture. In yet another embodiment, solutions of sources of M.sub.I, M.sub.I, M.sub.III, and M.sub.IV in protic solvent can be added simultaneously together with an alkyl quaternary ammonium hydroxide solution to form the reaction mixture. In one embodiment, the pH does not need to be adjusted.

(20) The reaction mixture, which may be a slurry, is then reacted at temperature in the range of about 25° C. to about 200° C., or from about 60° C. to about 180° C., or from about 80° C. to about 150° C. in a sealed autoclave reactor or in a reactor open to ambient pressure. The sealed autoclave reactor or the reactor open to ambient pressure can be equipped with a stirring device to mix the reaction mixture. In another embodiment, the sealed autoclave or the reactor open to the ambient pressure does not have a stirring device and the reaction is conducted at a static state unless the temperature of the reaction mixture is higher than boiling point of the mixture, causing autonomous stirring by the boiling of the reaction mixture. In embodiment where a reactor open to ambient pressure is employed, a reflux device can be optionally attached to the reactor to avoid solvent loss when the reaction temperature is close to or above the boiling temperature of the reaction mixture.

(21) The reaction time may range from about 0.5 to about 200 h, or 0.5 h to about 100 h, or from about 1 h to about 50 h, or from about 2 h to about 24 h. Optionally, the reaction mixture may be mixed continuously or intermittently during the reaction. In one embodiment, the reaction mixture is mixed every few hours. The mixed transition metal oxide material is recovered from the slurry.

(22) In a specific embodiment, the mixed transition metal oxide material may be present in a composition along with a binder, where the binder may be, for example, silicas, aluminas, silica-aluminas, titanias, zirconias, natural clays, synthetic clays, and mixtures thereof. The selection of binder includes but is not limited to, anionic and cationic clays such as hydrotalcites, pyroaurite-sjogrenite-hydrotalcites, montmorillonite and related clays, kaolin, sepiolites, silicas, aluminas such as (pseudo) boehomite, gibbsite, flash calcined gibbsite, eta-alumina, zirconia, titania, alumina coated titania, silica-alumina, silica coated alumina, alumina coated silicas and mixtures thereof, or other materials generally known as particle binders in order to maintain particle integrity. These binders may be applied with or without peptization. The binder may be added to the bulk mixed transition metal oxide material, or may be incorporated during synthesis. The amount of binder may range from about 1 to about 80 wt % of the finished composition, or from about 1 to about 30 wt % of the finished composition, or from about 5 to about 26 wt % of the finished composition. The binder may be chemically bound to the mixed transition metal oxide material, or may be present in a physical mixture with the novel mixed transition metal oxide material. The mixed transition metal oxide material maybe extruded or pelletized with or without a binder.

(23) At least a portion of the mixed transition metal oxide material, with or without a binder, or before or after inclusion of a binder, can be sulfided in situ in an application or pre-sulfided to form metal sulfides which in turn are used in an application. The sulfidation may be conducted under a variety of sulfidation conditions such as through contact of the mixed transition metal oxide material with a sulfur containing stream or feedstream as well as the use of a gaseous mixture of H.sub.2S/H.sub.2. The sulfidation of the mixed transition metal oxide material is performed at elevated temperatures, typically ranging from 50 to 600° C., or from 150 to 500° C., or from 250 to 450° C. The sulfiding step can take place at a location remote from other synthesis steps, remote from the location of the application where the mixed transition metal oxide material will be used, or remote from both the location of synthesis and remote from location of use. The materials resulting from the sulfiding step are referred to as metal sulfides which can be used as catalysts in conversion processes.

(24) As discussed, at least a portion of the mixed transition metal oxide material of this invention can be sulfided and the resulting metal sulfides used as catalysts in conversion processes such as hydrocarbon conversion processes. Hydroprocessing is one class of hydrocarbon conversion processes in which the mixed transition metal oxide material is useful as a catalyst. Examples of specific hydroprocessing processes are well known in the art and include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking. In one embodiment, a conversion process comprises contacting the mixed transition metal oxide material with a sulfiding agent to generate metal sulfides which are contacted with a feed stream at conversion conditions to generate at least one product.

(25) The operating conditions of the hydroprocessing processes listed above typically include reaction pressures from about 2.5 MPa to about 17.2 MPa, or in the range of about 5.5 to about 17.2 MPa, with reaction temperatures in the range of about 245° C. to about 440° C., or in the range of about 285° C. to about 425° C. Contact time for the feed and the active catalyst, referred to as liquid hourly space velocities (LHSV), should be in the range of about 0.1 h.sup.−1 to about 10 h.sup.−1, or about 0.25 h.sup.−1 to about 8.0 h.sup.−1. Specific subsets of these ranges may be employed depending upon the feedstock being used. For example, when hydrotreating a typical diesel feedstock, operating conditions may include from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about 410° C., from about 0.25 h.sup.−1 to about 5 h.sup.−1, and from about 84 Nm.sup.3 H.sub.2/m.sup.3 to about 850 Nm.sup.3 H.sub.2/m.sup.3 feed. Other feedstocks may include gasoline, naphtha, kerosene, gas oils, distillates, and reformate.

(26) Examples are provided below to describe the invention more completely. These examples are only by way of illustration and should not be interpreted as a limitation of the broad scope of the invention, which is set forth in the claims.

Example 1

(27) 31.97 g of TMAOH and 1.98 g of aluminum-sec-butoxide were set to stir in a beaker. Then, a solution containing 6.88 g ammonium heptamolybdate (AHM), 11.33 g nickel nitrate, and 107.91 g de-ionized water was added. The resulting slurry was stirred and digested at 100° C. for 22 h. The XRD-pattern of material generated in this example is shown in FIG. 1.

Example 2

(28) 719.23 g of TMAOH and 44.53 g of aluminum-sec-butoxide were set to stir in a beaker. Then, a solution containing 154.79 g AHM, 254.87 g nickel nitrate, and 2427.93 g de-ionized water was added. The resulting slurry was stirred and digested at 100° C. for 24 h. The composition of this material was 4.66% Al, 43.3% Ni, 26% Mo, and 16.6% LOI from ICP. The XRD-pattern of material generated in this example is shown in FIG. 2.

Example 3

(29) 719.23 g of TMAOH and 44.53 g of aluminum-sec-butoxide were set to stir in a beaker. Then, a solution containing 154.79 g AHM, 254.87 g nickel nitrate, and 2427.93 g de-ionized water was added. The resulting slurry was stirred and digested at 100° C. for 24 h. The XRD-pattern of material generated in this example is shown in FIG. 3.

Example 4

(30) 32.42 g of TMAOH and 1.33 g of a colloidal silica 40 wt.-% suspension in water (Ludox AS-40) were set to stir in a beaker. Then, a solution containing 9.28 g AHM, 7.70 g nickel nitrate, and 109.43 g de-ionized water was added. The resulting slurry was stirred and split into several portions digested at 100 or 175° C. The XRD-pattern of material generated in this example is shown in FIG. 4.

Example 5

(31) 32.12 g of TMAOH and 1.17 g of a colloidal silica 40 wt.-% suspension in water (Ludox AS-40) were set to stir in a beaker. Then, a solution containing 6.91 g AHM, 11.38 g Ni nitrate, and 108.42 g di-ionized water was added. The resulting slurry was stirred and digested at 100° C. for 24 h. The XRD-pattern of material generated in this example is shown in FIG. 5.

Example 6

(32) 722.62 g of TMAOH and 26.43 g of a colloidal silica 40 wt.-% suspension in water (Ludox AS-40) were set to stir in a beaker. Then, a solution containing 155.52 g AHM, 256.07 g Ni nitrate, and 2439.37 g de-ionized water was added. The resulting slurry was stirred and digested at 100° C. for 3 days. The XRD-pattern of material generated in this example is shown in FIG. 6.

Example 7

(33) 281.02 g of TMAOH and 10.28 g of a colloidal silica 40 wt.-% suspension in water (Ludox AS-40) were set to stir in a beaker. Then, a solution containing 60.48 g AHM, 99.58 g Ni nitrate, and 948.65 g de-ionized water was added. The resulting slurry was stirred and digested at 125° C. for 20 h. The XRD-pattern of material generated in this example is shown in FIG. 7.

(34) The recovered materials generated in Examples 1 through 7 were each analyzed by several analytical methods and determined to be within the formula and description set forth above and in the claims. Analytical methods included Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) as described in UOP Method 1020-17; Loss on Ignition (LOI) for Fresh, Regenerated, Used, and Spent Catalysts, Catalyst Supports, and Adsorbents as described in UOP Method 954; Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants as described in ASTM method D5291.

Embodiments

(35) A first embodiment is a mixed transition metal oxide material having the formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r
where:
M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4);
M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);
M.sub.III is a metal selected from Group VIB (IUPAC Group 6);
M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14);
[R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms and R1, R2, R3 and R4 can be the same or different from each other;
wherein m/(m+n)≥0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0,
wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0
wherein the material is further characterized by an X-ray diffraction pattern, which is essentially amorphous with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si:

(36) TABLE-US-00009 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s

(37) TABLE-US-00010 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s
wherein the listed peaks have a full width at half maximum greater than 0.75°. The first embodiment may comprise wherein the mixed transition metal oxide material is present in a mixture with at least one binder and wherein the mixture comprises up to 80 wt % binder. The binder may be selected from silicas, aluminas, silica-aluminas, titanias, zirconias, natural clays, synthetic clays, and mixtures thereof. M.sub.I may be Zr, Mn, Cu, Zn, or any mixture thereof. Mn may be Fe, Co, Ni, or any mixture thereof. M.sub.III may be Cr, Mo, or W. The first embodiment may comprise wherein the novel mixed transition metal oxide material is sulfided.

(38) A second embodiment is a method of making a mixed transition metal oxide material having the formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r where:

(39) M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4);

(40) M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);

(41) M.sub.III is a metal selected from Group VIB (IUPAC Group 6);

(42) M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14);

(43) [R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms and R1, R2, R3 and R4 can be the same or different from each other;

(44) wherein m/(m+n)≥0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0,

(45) wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0
wherein material is further characterized by an X-ray diffraction pattern, which is essentially amorphous with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si:

(46) TABLE-US-00011 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s

(47) TABLE-US-00012 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s
wherein the listed peaks have a full width at half maximum greater than 0.75°

(48) the method comprising: (a) adding sources of M.sub.I, M.sub.II, M.sub.III, and M.sub.IV, to at least one short-chain alkyl quaternary ammonium hydroxide compound having the formula [R1 R2 R3 R4-N]OH, where R1, R2, R3 and R4 are alkyl radicals having 1 to 6 carbon atoms, and R1, R2, R3 and R4 can be the same or different to form a reaction mixture wherein the reaction mixture does not contain additional NH.sub.3.H.sub.2O or other basic solutions; (b) reacting the reaction mixture at a temperature from about 25° C. to about 200° C. for a period of time from about 30 minutes to 200 hours to generate the mixed transition metal oxide material; and (c) recovering the mixed transition metal oxide material.
The second embodiment may comprise wherein the reaction mixture is a slurry. The second embodiment may further comprise adding a binder to the reaction mixture or to the recovered mixed transition metal oxide material. In the second embodiment the binder may be selected from aluminas, silicas, alumina-silicas, titanias, zirconias, natural clays, synthetic clays, and mixtures thereof. The second embodiment may further comprise sulfiding at least a portion of the recovered mixed transition metal oxide material. The second embodiment may comprise wherein the reacting is conducted under atmospheric pressure or autogenous pressure. The second embodiment may comprise wherein the recovering is by decantation, filtration, or centrifugation. The second embodiment may comprise continuous or intermittent mixing during the reacting, during the adding or both during the reacting and during the adding. The second embodiment wherein the temperature is varied during the reacting.

(49) A third embodiment is A conversion process comprising contacting a material with a sulfiding agent to convert at least a portion of the material to metal sulfides and contacting the metal sulfides with a feed at conversion conditions to generate at least one product, wherein the material comprises a mixed transition metal oxide material having the formula:
[R1R2R3R4-N].sub.x(NH.sub.4).sub.y(M.sub.I.sup.a).sub.m(M.sub.II.sup.b).sub.n(M.sub.III.sup.c).sub.o(M.sub.IV.sup.d).sub.pO.sub.q(OH).sub.r
where:

(50) M.sub.I is a metal or mixture of metals selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), and Group IVB (IUPAC Group 4);

(51) M.sub.II is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);

(52) M.sub.III is a metal selected from Group VIB (IUPAC Group 6);

(53) M.sub.IV is an element selected from Group IIIA (IUPAC Group 13) or Group IVA (IUPAC Group 14);

(54) [R1 R2 R3 R4-N] is a tetra-alkyl ammonium cation with one positive charge, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6 carbon atoms and R1, R2, R3 and R4 can be the same or different from each other;

(55) wherein m/(m+n)≤0 and m/(m+n)≤1, wherein (m+n)/o is from 1/10 to 10/1, wherein o>0,

(56) wherein x, p, and r are each greater than 0, wherein y is greater than or equal to 0, and a, b, c, d, x, y, m, n, o, p, q, and r satisfy the equation:
x*(+1)+y*(+1)+a*m+b*n+c*o+d*p+q*(−2)+r*(−1)=0
wherein the material is further characterized by an X-ray diffraction pattern, which is essentially amorphous with crystalline peaks shown in Table A if M.sub.IV is Al or Table S if M.sub.IV is Si:

(57) TABLE-US-00013 TABLE A 2θ (°) d (Å) 100(I/I.sub.o)  7.5-16.0 11.781-5.563  s-vs 18.5-30.0 4.742-2.995 m-s 32.0-41.5 2.793-2.181 vs 58.0-65.0 1.582-1.431 m-s

(58) TABLE-US-00014 TABLE S 2θ (°) d (Å) 100(I/I.sub.o) 5.50-11.0 14.981-7.981  w-m 32.0-36.5 2.746-2.476 vs 58.0-62.5 1.587-1.485 m-s
wherein the listed peaks have a full width at half maximum greater than 0.75°. The third embodiment may comprise wherein the conversion process is hydroprocessing. Third embodiment where the conversion process is hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, or hydrocracking. The third embodiment may comprise wherein the mixed transition metal oxide material is present in a mixture with at least one binder and wherein the mixture comprises up to about 80 wt % binder.