Mixed metal oxides

Abstract

A unique mixed metal molybdotungstate material has been developed. The material may be used as a hydroprocessing catalyst. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodearomatization, hydrodesilication, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

Claims

1. A mixed metal oxide material has the formula:
MMo.sub.xW.sub.yO.sub.z wherein M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5; y varies from 0.01 to 0.25; the sum of (x+y) must be <1.501; z is a number which satisfies the sum of the valences of M, Mo and W; the mixed metal oxide having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A: TABLE-US-00011 TABLE A d() 4.2-2.89 2.65-2.53 2.17-2.04 1.53-1.45.

2. The mixed metal oxide material of claim 1 wherein the mixed metal oxide is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

3. The mixed metal oxide material of claim 2 wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

4. The mixed metal oxide material of claim 1 wherein M is nickel or cobalt.

5. The mixed metal oxide material of claim 1 wherein M is nickel.

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

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the X-ray powder diffraction pattern of a crystalline bis-ammonia transition metal molybdotungstate pre-cursors prepared by boiling crystallization as described in Examples 1 to 3.

(2) FIG. 2 is the X-ray powder diffraction pattern of the mixed metal oxide, prepared by boiling crystallization followed by thermal decomposition as described in Examples 1 to 3.

DETAILED DESCRIPTION OF THE INVENTION

(3) The present invention relates to a unique mixed metal oxide material that has been produced and optionally sulfided, to yield an active hydroprocessing catalyst. The mixed metal oxide has been given the designation UPM-7. The mixed metal oxide material has the formula:
MMo.sub.xW.sub.yO.sub.z
wherein M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5, or between 0.6 to 1.3 or from 0.8 to 1.2; y varies from 0.01 to 0.25, or between 0.1 and 0.2; the sum of (x+y) must be 1.501, or 1.2; z is a number which satisfies the sum of the valences of M, Mo and W. The mixed metal oxide having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A.

(4) TABLE-US-00005 TABLE A d() 4.2-2.89 2.65-2.53 2.17-2.04 1.53-1.45

(5) The mixed metal oxide of the invention is further characterized by the x-ray powder diffraction pattern shown in the FIG. 2.

(6) The mixed metal oxide is prepared by thermal decomposition of a crystalline bis-ammonia transition metal molybdotungstate pre-cursor material having the formula:
(NH.sub.3).sub.2-nM(OH.sub.2).sub.nMo.sub.xW.sub.yO.sub.z
where n varies from 0.1 to 2.0; M represents a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5, or between 0.6 to 1.3 or from 0.8 to 1.2; y varies from 0.01 to 0.25, or between 0.1 and 0.2; the sum of (x+y) must be 1.501, or 1.2; z is a number which satisfies the sum of the valences of M, Mo and W; is formed. The crystalline bis-ammonia transition metal molybdotungstate pre-cursor material is further characterized by a unique x-ray powder diffraction pattern showing the crystalline peaks in Table B:

(7) TABLE-US-00006 TABLE B d() I/I.sub.0 % 7.49-7.28 vs 5.1-5.05 s 4.4-4.257 w 3.966-3.915 m 3.69-3.645 s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.097 w 3-2.97 m 2.76-2.73 m

(8) The pre-cursor material is prepared by solvothermal crystallization of a reaction mixture typically prepared by mixing reactive sources of molybdenum and tungsten with the appropriate metal M with a solvent as well as a source of ammonia. Specific examples of the molybdenum source which may be utilized in this invention include but are not limited to molybdenum trioxide, ammonium dimolybdate, ammonium thiomolybdate, and ammonium heptamolybdate. Specific examples of the tungsten source which may be utilized in this invention include but are not limited to tungsten trioxide, ammonium ditungstate, ammonium thiotungstate, and ammonium metatungstate. Sources of other metals M include but are not limited to the respective halide, acetate, nitrate, carbonate, thiols and hydroxide salts. Specific examples include nickel chloride, cobalt chloride, nickel bromide, cobalt bromide, magnesium chloride, zinc chloride, nickel nitrate, cobalt nitrate, iron nitrate, manganese nitrate, zinc nitrate, nickel acetate, cobalt acetate, iron acetate, nickel carbonate, cobalt carbonate, zinc hydroxide, nickel hydroxide and cobalt hydroxide.

(9) The source of ammonia may include but is not limited to ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, ammonium chloride, ammonium fluoride or a combination thereof.

(10) Generally, the process used to prepare the precursor material involves forming a reaction mixture wherein all of the components, such as for example, Ni, Mo, W, NH.sub.4OH and H.sub.2O are mixed in solution together. By way of example, a reaction mixture may be formed which in terms of molar ratios of the oxides is expressed by the formula:
AMO.sub.x:BMoO.sub.y:CWO.sub.z:D(NH.sub.3):H.sub.2O
where M is selected from the group consisting of iron, cobalt, nickel, manganese, copper, zinc and mixtures thereof; A represents the molar ratio of M and may vary from 0.1 to 3, or from 0.75 to 2, or from 1 to 1.5; x is a number which satisfies the valency of B represents the molar ratio of Mo and may vary from 0.1 to 3, or from 0.75 to 2, or from 1 to 1.5; y is a number which satisfies the valency of Mo; C represents the molar ratio of W and may vary from 0.01 to 2, or from 0.05 to 1, or from 0.2 to 0.75; z is a number which satisfies the valency of W; D represents the molar ratio of NH.sub.3 and may vary from 0.5 to 15 or from 1 to 10 or from 3 to 7; the molar ratio of H.sub.2O, varies from 0.1 to 1000, or from 1 to 300, or from 1 to 100.

(11) It is necessary to adjust the pH of the mixture to a value of from about 8.5 to about 10. The pH of the mixture can be controlled through the addition of a base such as NH.sub.4OH, quaternary ammonium hydroxides, amines, and the like.

(12) Once the reaction mixture is formed, the reaction mixture is reacted at temperatures ranging from about 60 C. to about 250 C. for a period of time ranging from 30 minutes to around 14 days hours. In one embodiment the temperature range for the reaction is from about 70 C. to about 180 C. and in another embodiment the temperature range of from about 80 C. to about 140 C. In one embodiment, the reaction time is from about 1 hour to about 48 hours, and in another embodiment the reaction time is from about 2 hours to about 12 hours. The reaction is carried out under atmospheric pressure or in a sealed vessel under autogenous pressure. In one embodiment the synthesis may be conducted in an open vessel under reflux conditions. A crystalline bis-ammonia transition metal molybdotungstate pre-cursor material is formed and may be characterized by a unique x-ray powder diffraction pattern as shown in Table B above.

(13) Once formed, the crystalline bis-ammonia transition metal molybdotungstate may have a binder incorporated, where 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, alumina such as (pseudo) boehomite, gibbsite, flash calcined gibbsite, eta-alumina, zicronica, 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 crystalline bis-ammonia metal molybdate pre-cursor material, and the amount of binder may range from about 1 to about 30 wt % of the finished catalysts or from about 5 to about 26 wt % of the finished catalyst. The binder may be chemically bound to the crystalline bis-ammonia transition metal molybdotungstate precursor material, or may be present in a physical mixture with the crystalline bis-ammonia transition metal molybdotungstate precursor.

(14) The crystalline bis-ammonia transition metal molybdotungstate precursor, with or without an incorporated binder can then be optionally sulfided or pre-sulfided under a variety of sulfidation conditions, these include through contact of the crystalline bis-ammonia transition metal molybdotungstate precursor with a sulfur containing feed as well as the use of a gaseous mixture of H.sub.2S/H.sub.2. The sulfidation of the crystalline bis-ammonia transition metal molybdotungstate precursor is performed at elevated temperatures, typically ranging from 50 to 600 C., or from 150 to 500 C., most or from 250 to 450 C.

(15) Once formed, the crystalline bis-ammonia metal molybdate pre-cursor is thermally decomposed to form the mixed metal oxide of the invention which in turn may be used as a catalyst in a variety of hydroprocessing processes. The thermal decomposition may be conducted in air, or other suitable environments, at temperatures from about 275 C. to about 350 C., or from about 290 C. to about 320 C. and for about 1 to about 24 hours; or for about 1 to about 8 hours; or from about 1 to about 4 hours. Decomposition products from these one-dimensional chains of the pre-cursor may result in one-dimensional chains or a two dimensional network i.e. layers or a three dimensional framework solid.

(16) If the crystalline bis-ammonia metal molybdate pre-cursor did not have a binder incorporated, or was not sulfided, either may be performed after the thermal decomposition of the crystalline bis-ammonia metal molybdate pre-cursor and formation of the mixed metal oxide. If the crystalline bis-ammonia metal molybdate pre-cursor did have a binder incorporated, or was already sulfided, additional binder may be added or additional sulfiding may be conducted. The mixed metal oxide may have a binder incorporated, including but not limited to silica, alumina, silica-alumina and mixtures thereof, or other materials generally known as particle binders in order to maintain particle integrity. The binder may be added to the bulk mixed metal oxide, and the amount of binder may range from about 1 to about 30 wt % of the finished catalysts or from about 5 to about 26 wt % of the finished catalyst. The binder may be chemically bound to the mixed metal oxide decomposition product, or may be present in a physical mixture with the mixed metal oxide.

(17) The unsupported mixed metal oxide of this invention can be used as a catalyst or catalyst support in various hydrocarbon conversion processes. Hydroprocessing processes is one class of hydrocarbon conversion processes in which the crystalline bis-ammonia metal molybdate material is useful as a catalyst. Examples of specific hydroprocessing processes are well known in the art and include hydrotreating or hydrofining, hydrogenation, hydrodearomatization, hydrodemetallation, hydrodesilication hydrocracking, hydrodenitrogenation, and hydrodesulfurization.

(18) 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. Time with which the feed is in contact with the active catalyst, referred to as liquid hour space velocities (LHSV), should be in the range of about 0.1 h.sup.1 to about 10 h.sup.1, or about 2.0 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 to about 5/h, and from about 84 Nm3 H2/m3 to about 850 Nm3 H2/m3 feed. Other feedstocks may include gasoline, naphtha, kerosene, gas oils, distillates, and reformate.

(19) Examples are provided below so that the invention may be described 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 appended claims.

(20) Patterns presented in the following examples were obtained using standard x-ray powder diffraction techniques. The radiation source was a high-intensity, x-ray tube operated at 45 kV and 35 mA. The diffraction pattern from the copper K-alpha radiation was obtained by appropriate computer based techniques. Powder samples were pressed flat into a plate and continuously scanned from 3 and 70 (2). Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as , where is the Bragg angle as observed from digitized data. Intensities were determined from the integrated area of diffraction peaks after subtracting background, I.sub.O being the intensity of the strongest line or peak, and I being the intensity of each of the other peaks. As will be understood by those skilled in the art the determination of the parameter 2 is subject to both human and mechanical error, which in combination can impose an uncertainty of about 0.4 on each reported value of 2. This uncertainty is also translated to the reported values of the d-spacings, which are calculated from the 2 values. In some of the x-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, and w, which represent very strong, strong, medium, and weak, respectively. In terms of 100(I/I.sub.0), the above designations are defined as:

(21) w=0-15, m=15-60: s=60-80 and vs=80-100.

(22) In certain instances the purity of a synthesized product may be assessed with reference to its x-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the x-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present. As will be understood to those skilled in the art, it is possible for different poorly crystalline materials to yield peaks at the same position. If a material is composed of multiple poorly crystalline materials, then the peak positions observed individually for each poorly crystalline materials would be observed in the resulting summed diffraction pattern. Likewise it is possible to have some peaks appear at the same positions within different, single phase, crystalline materials, which may be simply a reflection of a similar distance within the materials and not that the materials possess the same structure.

Example 1

(23) In a ceramic dish, 15.21 g of nickel carbonate (0.15 moles Ni), 13.24 g ammonium heptamolybdate (0.075 moles Mo), and 18.20 g of ammonium metatungstate (0.075 moles of W) were added to 25 ml of concentrated ammonium hydroxide solution. The solution was dried at 150 C for 18 hours with periodic mixing. The dried residue was analyzed by x-ray powder diffraction as described above, and the X-ray powder diffraction pattern is shown in FIG. 1. The dried residue was then calcined in air at a temperature of about 300 C. for 2 hours and then cooled. The calcined material was analyzed by x-ray powder diffraction as described above, and the X-ray powder diffraction pattern of the calcined material is shown in FIG. 2.

Example 2

(24) Solution A. In a 3 liter flask, 35.61 g of nickel carbonate (0.3 moles Ni) and 28.79 g molybdenum trioxide (0.2 moles Mo) were added to 300 ml of water forming a slurry. Solution B. In a 500 ml flask, 13.05 g of ammonium metatungstate (0.05 moles W) was added to 90 ml of a concentrated NH.sub.4OH solution. Solution B was added to solution A before being refluxed at about 100 C. During the heating the precipitates dissolved to give a clear deep blue solution prior to the formation of a lime green precipitate. After about 2 hours, a green precipitate was observed suspended in the blue about pH 9 solution. This precipitate was cooled to room temperature, filtered, washed with 90 ml of about 90 C. water and then dried at 100 C. The X-ray powder diffraction of the dried precipitate is shown in FIG. 1. The dried precipitate was then calcined in air at a temperature of 275 C. for 2 hours then cooled. The X-ray powder diffraction of the calcined material is shown in FIG. 2.

Example 3

(25) Solution A. In a 3 liter flask, 35.61 g of nickel carbonate (0.3 moles Ni) and 28.79 g molybdenum trioxide (0.2 moles Mo) were added to 300 ml of water forming a slurry. Solution B. In a 500 ml flask, 26.1 g of ammonium metatungstate (0.1 moles W) was added to 90 ml of a concentrated NH.sub.4OH solution. Solution B was added to solution A before being refluxed at about 100 C. During the heating the precipitates dissolved to give a clear deep blue solution prior to the formation of a lime green precipitate. After about 3 hours, a green precipitate was observed suspended in the blue about pH 9 solution. This precipitate was cooled to room temperature, filtered, washed with 90 ml of about 90 C. water and then dried at 100 C. The X-ray powder diffraction of the dried precipitate is shown in FIG. 1. The dried precipitate was then calcined in air at a temperature of about 300 C. for 2 hours and then cooled. The X-ray powder diffraction of the calcined material is shown in FIG. 2.

Embodiments

(26) Embodiment 1 is mixed metal oxide material having the formula:
MMo.sub.xW.sub.yO.sub.z
wherein M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5, or between 0.6 to 1.3 or from 0.8 to 1.2; y varies from 0.01 to 0.25, or between 0.1 and 0.2; the sum of (x+y) must be 1.501, or 1.2; z is a number which satisfies the sum of the valences of M, Mo and W. The mixed metal oxide having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

(27) TABLE-US-00007 TABLE A d() 4.2-2.89 2.65-2.53 2.17-2.04 1.53-1.45

(28) The mixed metal oxide of embodiment 1 wherein the mixed metal oxide is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

(29) The mixed metal oxide of embodiment 1 wherein the mixed metal oxide is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder and wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

(30) The mixed metal oxide of embodiment 1 wherein M is nickel or cobalt.

(31) The mixed metal oxide of embodiment 1 wherein M is nickel.

(32) The mixed metal oxide of embodiment 1 wherein the mixed metal oxide is sulfided.

(33) Embodiment 2 is a method of making a mixed metal oxide having the formula:
MMo.sub.xW.sub.yO.sub.z
wherein M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5, or between 0.6 to 1.3 or from 0.8 to 1.2; y varies from 0.01 to 0.25, or between 0.1 and 0.2; the sum of (x+y) must be 1.501, or 1.2; z is a number which satisfies the sum of the valences of M, Mo and W. The mixed metal oxide having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

(34) TABLE-US-00008 TABLE A d() 4.2-2.89 2.65-2.53 2.17-2.04 1.53-1.45
the method comprising: (a) forming a reaction mixture containing sources of M, W, and Mo; adjusting the pH of the reaction mixture to a pH of from about 8.5 to about 10; (b) adjusting the pH of the reaction mixture to a pH of from about 8.5 to about 10; (c) heating the solution to between 85 and 100 C. until the resultant pH is between 8.5 and 9.5; and (d) recovering a crystalline bis-ammonia transition metal molybdotungstate precursor having the formula:
(NH.sub.3).sub.2-nM(OH.sub.2).sub.nMo.sub.xW.sub.yO.sub.z
where n varies from 0.1 to 2.0; M represents a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5, or between 0.6 to 1.3 or from 0.8 to 1.2; y varies from 0.01 to 0.25, or between 0.1 and 0.2; the sum of (x+y) must be 1.501, or 1.2; z is a number which satisfies the sum of the valences of M, Mo and W; is formed. The crystalline bis-ammonia transition metal molybdotungstate pre-cursor material is further characterized by a unique x-ray powder diffraction pattern showing the crystalline peaks in Table B:

(35) TABLE-US-00009 TABLE B d() I/I.sub.0 % 7.49-7.28 vs 5.1-5.05 s 4.4-4.257 w 3.966-3.915 m 3.69-3.645 s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.097 w 3-2.97 m 2.76-2.73 m
(e) heating the crystalline bis-ammonia transition metal molybdotungstate precursor at a temperature of from about 275 C. to about 350 C. for about 1 to about 24 hours; and (f) recovering the mixed metal oxide.

(36) The method of embodiment 2 wherein the recovering is by filtration or centrifugation.

(37) The method of embodiment 2 further comprising adding a binder to the recovered bis-ammonia transition metal molybdotungstate precursor material or to the recovered mixed metal oxide or both.

(38) The method of embodiment 2 further comprising adding a binder to the recovered bis-ammonia transition metal molybdotungstate precursor material or to the recovered mixed metal oxide or both and wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.

(39) The method of embodiment 2 further comprising sulfiding the recovered bis-ammonia transition metal molybdotungstate precursor material or the recovered mixed metal oxide or both.

(40) Embodiment 3 is a conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising a mixed metal oxide material having the formula:
MMo.sub.xW.sub.yO.sub.z
wherein M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; x varies from 0.5 to 1.5, or between 0.6 to 1.3 or from 0.8 to 1.2; y varies from 0.01 to 0.25, or between 0.1 and 0.2; the sum of (x+y) must be 1.501, or 1.2; z is a number which satisfies the sum of the valences of M, Mo and W. The mixed metal oxide having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

(41) TABLE-US-00010 TABLE A d() 4.2-2.89 2.65-2.53 2.17-2.04 1.53-1.45

(42) The process of embodiment 3 wherein the conversion process is hydroprocessing.

(43) The process of embodiment 3 where the conversion process is selected from the group consisting of hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodearomatization, hydroisomerization, hydrodesilication, hydrotreating, hydrofining, and hydrocracking

(44) The process of embodiment 3 wherein the mixed metal oxide is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

(45) The process of embodiment 3 wherein the mixed metal oxide is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder and wherein the binder is selected from silicas, aluminas, and silica-aluminas.

(46) The process of embodiment 3 wherein the mixed metal oxide is sulfided.