Transition metal tungsten oxy-hydroxide

Abstract

A hydroprocessing catalyst or catalyst precursor has been developed. The catalyst is a unique transition metal tungsten oxy-hydroxide material. The hydroprocessing using the transition metal tungsten oxy-hydroxide material or the decomposition product thereof may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

Claims

1. A conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising the decomposition product of the decomposition by sulfidation of a metal tungsten oxy-hydroxide material having the formula:
S.sub.a(NH.sub.4).sub.bM(OH).sub.xW.sub.yO.sub.z where S is a sugar selected from glucose, fructose, galactose, lactose, maltose, sucrose, and mixtures thereof; a varies from 0.001 to 5; b varies from 0.1 and 3 M is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn, and combinations thereof; x varies from 0.1 to 2; y varies from 0.1 to 4; z is a number which satisfies the sum of the valences of M, b, x and y; the material having a poorly crystalline diffraction pattern showing a broad peak between d-spacing 4.45-2.25 .

2. The process of claim 1 wherein the conversion process is hydroprocessing.

3. The process of claim 1 wherein the conversion process is selected from the group consisting of hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

4. The process of claim 1 wherein the transition metal tungsten oxy-hydroxide material, or the decomposition product, or both, are present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

5. The process of claim 4 wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

6. The process of claim 1 wherein the feed comprises sulfur and the decomposition by sulfidation comprises contacting the metal tungsten oxy-hydroxide material with the sulfur containing feed.

7. The process of claim 1 wherein the decomposition by sulfidation comprises contacting the metal tungsten oxy-hydroxide material with a gaseous mixture of H.sub.2S/H.sub.2.

8. The process of claim 1 wherein the sulfidation is conducted at a temperature ranging from about 50 C. to about 600 C.

9. The process of claim 1 wherein the sulfidation is conducted at a temperature ranging from about 150 C. to about 500 C.

10. The process of claim 1 wherein the sulfidation is conducted at a temperature ranging from about 250 C. to about 450 C.

11. A method of making a catalyst comprising the decomposition product of the decomposition by sulfidation of transition metal tungsten oxy-hydroxide material having the formula:
S.sub.a(NH.sub.4).sub.bM(OH).sub.xW.sub.yO.sub.z where S is a sugar selected from glucose, fructose, galactose, lactose, maltose, sucrose, and mixtures thereof; a varies between 0.001 to 5; b varies from 0.1 and 3 M is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn, and combinations thereof; x varies from 0.1 to 2; y varies from 0.1 to 4; z is a number which satisfies the sum of the valences of M, b, x and y; the material having a poorly crystalline diffraction pattern showing a broad peak between d-spacing 4.45-2.25 , the method comprising: (a) forming a reaction mixture containing NH.sub.3, H.sub.2O, and sources of S, M, and W; (b) adjusting the pH of the reaction mixture to a pH of from about 8.5 to about 10; (c) reacting the reaction mixture; (d) recovering the transition metal tungsten oxy-hydroxide material; and (e) decomposing the recovered transition metal tungsten oxy-hydroxide material by sulfidation to generate at least one decomposition product.

12. The method of claim 11 wherein the reacting is conducted at a temperature ranging from about 60 C. to about 120 C. for a period of time ranging from 30 minutes to around 2 days.

13. The method of claim 11 wherein the recovering is by filtration or centrifugation.

14. The method of claim 11 further comprising adding a binder to the recovered metal tungsten oxy-hydroxide material.

15. The method of claim 14 wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The FIGURE is the X-ray powder diffraction pattern of the unique transition metal tungsten oxy-hydroxide, as represented by Examples 1-3.

DETAILED DESCRIPTION OF THE INVENTION

(2) The present invention relates to a unique transition metal tungsten oxy-hydroxide, a process for preparing the composition, and a process using the composition as the catalyst. The material has the designation UPM-14. This composition has an empirical formula:
S.sub.a(NH.sub.4).sub.bM(OH).sub.xW.sub.yO.sub.z
where S is a sugar selected from glucose, fructose, galactose lactose, maltose, sucrose, and mixtures thereof; a varies between 0.001 to 5, or between 0.1 and 3 or from 0.5 to 2; b varies between 0.1 and 3 M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; x varies from 0.1 to 2; y varies from 0.1 to 4 or from 0.5 to 2 or from 0.8 to 1.25; z is a number which satisfies the sum of the valences of M, b, x and y.

(3) The composition of the invention is characterized by having an extended network of M-O-M and M-(OH)-M linkages, where M represents a metal, or combination of metals listed above. The structural units repeat itself into at least two adjacent unit cells without termination of the bonding. The composition can have a one-dimensional network, such as for example, linear chains.

(4) The unique transition metal tungsten oxy-hydroxide is further characterized by its x-ray powder diffraction pattern showing a lack of crystallinity, characterized by a broad peak between 4.45-2.25 .

(5) The transition metal tungsten oxy-hydroxide of the invention having the x-ray powder diffraction pattern shown in the FIGURE.

(6) The transition metal tungsten oxy-hydroxide composition is prepared by solvothermal crystallization of a reaction mixture typically prepared by mixing reactive sources of tungsten with the appropriate metal M with a solvent as well as a source of ammonia and mono or disaccharide (cyclic or acylic). 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, ammonium heptatungstate, ammonium paratungstate 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, nickel nitrate, cobalt nitrate, iron nitrate, manganese nitrate, zinc nitrate, nickel acetate, cobalt acetate, iron acetate, nickel carbonate, cobalt carbonate, zinc carbonate, nickel hydroxide and cobalt hydroxide.

(7) 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.

(8) The source of S is a saccharide (mono or di) and may include, but is not limited to glucose, fructose, galactose lactose, maltose or sucrose or a combination thereof.

(9) Generally, the process used to prepare the composition of this invention involves forming a reaction mixture wherein all of the components, such as for example, S, M, W, NH.sub.4OH and H.sub.2O are mixed in solution together. By way of one specific example, a reaction mixture may be formed which in terms of molar ratios of the oxides is expressed by the formula:
S:AMO.sub.x:BWO.sub.y:C(NH.sub.3):H.sub.2O
where S can be glucose, fructose, galactose, lactose, maltose, sucrose and mixtures thereof, the molar ratio of S can vary from 0.001 to 2, or between 0.01 to 1, or from 0.1 to 1; 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 varies from 0.1 to 2 or from 0.5 to 1.5, or from 0.75 to 1; x satisfies the valency of M; B represents the molar ratio of W and varies from 0.1 to 3 or from 0.5 to 2, or from 0.75 to 1.25; y is a number which satisfies the valency of W; C is the molar ratio of NH.sub.3 and varies from 0.01 to 100 or from 1 to 50 or from 5 to 20; the molar ratio of H.sub.2O may vary from 1 to 900, or from 10 to 600, or from 50 to 300.

(10) 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.

(11) Once the reaction mixture is formed, the reaction mixture is reacted at temperatures ranging from about 60 C. to about 120 C. for a period of time ranging from 30 minutes to around 2 days. 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. The transition metal tungsten oxy-hydroxide is characterized by the x-ray powder diffraction pattern shown in the FIGURE.

(12) Once formed, the transition metal tungsten oxy-hydroxide 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 ammonia metal molybdate composition, 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 transition metal tungsten oxy-hydroxide, or may be present in a physical mixture with the transition metal tungsten oxy-hydroxide.

(13) The transition metal tungsten oxy-hydroxide, with or without an incorporated binder can then be sulfided or pre-sulfided under a variety of sulfidation conditions, these include through contact of the transition metal tungsten oxy-hydroxide with a sulfur containing feed as well as the use of a gaseous mixture of H.sub.2S/H.sub.2. The sulfidation of transition metal tungsten oxy-hydroxide 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.

(14) The unsupported transition metal tungsten oxy-hydroxide material of this invention can be used as a catalyst or catalyst support in various hydrocarbon conversion processes. Hydroprocessing is one class of hydrocarbon conversion processes in which the crystalline ammonia metal molybdate 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.

(15) 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 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.

(16) 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.

(17) 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. 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.

(18) In certain instances the purity of a synthesized product may be assessed with reference to its x-ray powder powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the x-ray powder pattern of the sample is free of lines attributable to crystalline impurities. As will be understood to those skilled in the art, it is possible for different poorly crystalline materials to yield a 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

(19) In a 1 liter flask, 25.4 g of ammonium metatungstate (0.1 moles of W) was dissolved in 160 g of deionized H.sub.2O and 40 ml of concentrated ammonium hydroxide. To this solution, 18.01 g of glucose (0.1 mole) was added to yield a clear solution, Solution A. Solution B was prepared where 29.08 g of nickel nitrate hexahydrate (0.1 moles of Ni) was completely dissolved in 50 g of deionized H.sub.2O. Solution B was added to solution A over a period of 10 minutes, resulting in the formation of a light blue slurry which was then refluxed at about 100 C. for 4 hours, forming a green precipitate. This precipitate was cooled to room temperature, filtered, washed with 90 ml of about 90 C. water and then dried at 100 C. X-ray powder diffraction of the dried precipitate matches the spectra shown in the FIGURE.

Example 2

(20) In a 1 liter flask, 20.32 g of ammonium metatungstate (0.08 moles of W) was dissolved in 160 g of deionized H.sub.2O and 40 ml of concentrated ammonium hydroxide. To this solution, 9 g of glucose (0.05 mole) was added to yield a clear solution, Solution A. Solution B was prepared where 29.08 g of nickel nitrate hexahydrate (0.1 moles of Ni) was completely dissolved in 50 g of deionized H.sub.2O. Solution B was added to solution A over a period of 10 minutes, resulting in the formation of a light blue slurry which was then refluxed at about 100 C. for 4 hours, forming a green precipitate. This precipitate was cooled to room temperature, filtered, washed with 90 ml of about 90 C. water and then dried at 100 C. X-ray powder diffraction of the dried precipitate matches the spectra shown in the FIGURE.

Example 3

(21) In a 1 liter flask, 20.32 g of ammonium metatungstate (0.08 moles of W) was dissolved in 160 g of deionized H.sub.2O and 40 ml of concentrated ammonium hydroxide. To this solution, 4.5 g of glucose (0.025 mole) was added to yield a clear solution, Solution A. Solution B was prepared where 23.7 g of cobalt chloride (0.1 moles of Co) was completely dissolved in 50 g of deionized H.sub.2O. Solution B was added to solution A over a period of 10 minutes, resulting in the formation of a light blue slurry which was then refluxed at about 100 C. for 4 hours, forming a precipitate. This precipitate was cooled to room temperature, filtered, washed with 90 ml of about 90 C. water and then dried at 100 C. X-ray powder diffraction of the dried precipitate matches the spectra shown in the FIGURE.

Embodiments

(22) Embodiment 1 is a transition metal tungsten oxy-hydroxide material having the formula:
S.sub.a(NH.sub.4).sub.bM(OH).sub.xW.sub.yO.sub.z
where S is a sugar selected from glucose, fructose, galactose lactose, maltose, sucrose, and mixtures thereof; a varies between 0.001 to 5, or between 0.1 and 3 or from 0.5 to 2; b varies between 0.1 and 3 M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; x varies from 0.1 to 2; y varies from 0.1 to 4 or from 0.5 to 2 or from 0.8 to 1.25; z is a number which satisfies the sum of the valences of M, b, x and y; the material having a poorly crystalline diffraction pattern showing a broad peak between d-spacing 4.45-2.25 .

(23) The transition metal tungsten oxy-hydroxide material of embodiment 1 wherein the transition metal tungsten oxy-hydroxide material is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

(24) The transition metal tungsten oxy-hydroxide material of embodiment 1 wherein the transition metal tungsten oxy-hydroxide material is present in a mixture with at least one binder, 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.

(25) The transition metal tungsten oxy-hydroxide material of embodiment 1 wherein M is nickel or cobalt.

(26) The transition metal tungsten oxy-hydroxide material of embodiment 1 wherein M is nickel.

(27) The transition metal tungsten oxy-hydroxide material of embodiment 1 wherein the transition metal tungsten oxy-hydroxide material is sulfided.

(28) Embodiment 2 is a method of making a transition metal tungsten oxy-hydroxide material having the formula:
S.sub.a(NH.sub.4).sub.bM(OH).sub.xW.sub.yO.sub.z
where S is a sugar selected from glucose, fructose, galactose lactose, maltose, sucrose, and mixtures thereof; a varies between 0.001 to 5, or between 0.1 and 3 or from 0.5 to 2; b varies between 0.1 and 3 M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; x varies from 0.1 to 2; y varies from 0.1 to 4 or from 0.5 to 2 or from 0.8 to 1.25; z is a number which satisfies the sum of the valences of M, b, x and y; the material having a poorly crystalline diffraction pattern showing a broad peak between d-spacing 4.45-2.25 , the method comprising: (a) forming a reaction mixture containing NH.sub.3, H.sub.2O, and sources of S, M, and W; (b) adjusting the pH of the reaction mixture to a pH of from about 8.5 to about 10; (c) reacting the reaction mixture; and (d) recovering the transition metal tungsten oxy-hydroxide material.

(29) The method of embodiment 2 wherein the reacting is conducted at a temperature ranging from about 60 C. to about 120 C. for a period of time ranging from 30 minutes to around 2 days.

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

(31) The method of embodiment 2 further comprising adding a binder to the recovered metal tungsten oxy-hydroxide material.

(32) The method of embodiment 2 further comprising adding a binder to the recovered metal tungsten oxy-hydroxide material wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.

(33) The method of embodiment 2 further comprising sulfiding the recovered transition metal tungsten oxy-hydroxide material.

(34) 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 metal tungsten oxy-hydroxide material having the formula:
S.sub.a(NH.sub.4).sub.bM(OH).sub.xW.sub.yO.sub.z
where S is a sugar selected from glucose, fructose, galactose lactose, maltose, sucrose, and mixtures thereof; a varies between 0.001 to 5, or between 0.1 and 3 or from 0.5 to 2; b varies between 0.1 and 3 M is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; x varies from 0.1 to 2; y varies from 0.1 to 4 or from 0.5 to 2 or from 0.8 to 1.25; z is a number which satisfies the sum of the valences of M, b, x and y; the material having a poorly crystalline diffraction pattern showing a broad peak between d-spacing 4.45-2.25 .

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

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

(37) The process of embodiment 3 wherein the transition metal tungsten oxy-hydroxide material is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

(38) The process of embodiment 3 wherein the transition metal tungsten oxy-hydroxide material is sulfided.