WO2017106133A1 - Crystalline transition metal oxy-hydroxide molybdotungstate - Google Patents

Crystalline transition metal oxy-hydroxide molybdotungstate Download PDF

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Publication number
WO2017106133A1
WO2017106133A1 PCT/US2016/066274 US2016066274W WO2017106133A1 WO 2017106133 A1 WO2017106133 A1 WO 2017106133A1 US 2016066274 W US2016066274 W US 2016066274W WO 2017106133 A1 WO2017106133 A1 WO 2017106133A1
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WO
WIPO (PCT)
Prior art keywords
transition metal
varies
crystalline transition
metal oxy
hydroxide molybdotungstate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2016/066274
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French (fr)
Inventor
Stuart Miller
Susan C. Koster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
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UOP LLC
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Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Priority to KR1020187019527A priority Critical patent/KR102116193B1/en
Priority to JP2018531074A priority patent/JP2019505463A/en
Priority to NZ74225116A priority patent/NZ742251A/en
Priority to CN201680073280.6A priority patent/CN108367941B/en
Priority to CA3004607A priority patent/CA3004607C/en
Priority to EP16876464.5A priority patent/EP3390282A4/en
Priority to RU2018125259A priority patent/RU2698819C1/en
Publication of WO2017106133A1 publication Critical patent/WO2017106133A1/en
Priority to SA518391650A priority patent/SA518391650B1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/02—Crystallisation from solutions
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Definitions

  • This invention relates to a new hydroprocessing catalyst. More particularly this invention relates to a unique crystalline transition metal oxy-hydroxide molybdotungstate and its use as a hydroprocessing catalyst.
  • the hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.
  • hydrodenitrification - HDN hydrodenitrification - HDN containing compounds from fuel feed stocks is targeted during the hydrotreating steps of refining and is achieved by the conversion of organic nitrogen and sulfur to ammonia and hydrogen sulfide respectively.
  • the structural chemistry of the tri-metallic mixed metal oxide material was likened to the hydrotalcite family of materials, referring to literature articles detailing the synthesis and characterization of a layered nickel molybdate material, stating that the partial substitution of molybdenum with tungsten leads to the production of a broadly amorphous phase which, upon decomposition by sulfidation, gives rise to superior hydrotreating activities.
  • E can be H 4 + , Na + or K + and M can be Zn 2+ , Co 2+ or Ni 2+ .
  • This material was reacted with a solution of ammonium heptamolybdate at room temperature to produce a highly crystalline compound, the structure of which could not be determined through conventional ab-initio methods.
  • the material was indexed, yielding crystallographic parameters which were the same as that of an ammonium nickel molybdate, reported by Astier, see example M. P. Astier, G. Dji, S. Teichner, J. Ann. Chim. (Paris), 1987, 12, 337, a material belonging to a family of ammonium-amine-nickel-molybdenum oxides closely related to Pezerat's materials.
  • a unique crystalline transition metal oxy-hydroxide molybdotungstate material has been produced and optionally sulfided, to yield an active hydroprocessing catalyst.
  • the crystalline transition metal oxy-hydroxide molybdotungstate material has a unique x-ray powder diffraction pattern showing strong peaks at 9.65, 7.3 and 5.17A.
  • the crystalline transition metal oxy-hydroxide molybdotungstate material has the formula:
  • Another embodiment involves a method of making a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
  • a varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;
  • 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof;
  • 'b' varies from 0.1 to 2;
  • 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2;
  • 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be ⁇ 1.501, or ⁇ 1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A: TABLE A
  • the method comprising forming a reaction mixture containing H 3 , H2O, and sources of M, W, and Mo; adjusting the pH of the reaction mixture to a pH of from 8.5 to 10; reacting the mixture together at elevated temperature with an autogenous pressure and then recovering the crystalline transition metal oxy-hydroxide molybdotungstate material.
  • the reacting may be conducted at a temperature of from 70°C to 200°C for a period of time from 30 minutes to 14 days.
  • Yet another embodiment involves a conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising: a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
  • ( H 4 )AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be ⁇ 1.501, or ⁇ 1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
  • FIG. 1 is the x-ray powder diffraction pattern of a crystalline transition metal oxy-hydroxide molybdotungstate prepared by boiling crystallization as described in Examples 1 to 3.
  • the present invention relates to a crystalline transition metal oxy-hydroxide molybdotungstate material and a process for preparing the material.
  • the material has the designation UPM-9.
  • the crystalline transition metal oxy-hydroxide molybdotungstate material has an empirical formula: ( H 4 )AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be ⁇ 1.501, or ⁇ 1.2 'z' is a number which satisfies the sum of the valency of a, M, b,
  • the crystalline composition of the invention is characterized by having an extended network of M-O-M, where M represents a metal, or combination of metals listed above.
  • 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.
  • the crystalline transition metal oxy-hydroxide molybdotungstate composition of the invention having the x-ray powder diffraction pattern shown in FIG. 1.
  • the crystalline transition metal oxy-hydroxide molybdotungstate composition is prepared by solvothermal crystallization of a reaction mixture typically prepared by mixing reactive sources of molybdenum and tungsten 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
  • 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.
  • 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.
  • 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.
  • the solvothermal process used to prepare the composition of this invention involves forming a reaction mixture wherein all of the components, such as for example, Ni, Mo, H 3 and H2O are mixed in solution together.
  • a reaction mixture may be formed which in terms of molar ratios of the oxides is expressed by the formula:
  • '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 3 or from 0.5 to 2 or from 0.75 to 1.25;
  • 'x' is a number which satisfies the valency of 'M';
  • 'B' represents the molar ratio of 'Mo' and varies from 0.1 to 3 or from 0.5 to 2 or from 0.75 to 1.25;
  • 'y' is a number satisfies the valency of 'Mo';
  • 'B' represents the molar ratio of 'W and varies from 0.01 to 1 or from 0.05 to 0.8 or from 0.1 to 0.6;
  • 'D' represents the molar ratio of H 3 and varies from 0.01 to 50 or from
  • the pH of the mixture is adjusted to a value ranging from 7.5 to 11, or from 8.5 to 10.
  • the pH of the mixture can be controlled through the addition of a base such as ⁇ 4 ⁇ , quaternary ammonium hydroxides, amines, and the like.
  • the reaction mixture is reacted at temperatures ranging from 70°C to 230°C for a period of time ranging from 30 minutes to around 14 days.
  • the temperate range for the reaction is from 110°C to 120°C and in another embodiment the temperature is in the range of from 150°C to 180°C.
  • the reaction time is from 4 to 6 hours, and in another embodiment the reaction time is from 7 to 10 days.
  • 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 crystalline transition metal oxy- hydroxide molybdotungstate compositions are recovered as the reaction product.
  • the crystalline transition metal oxy-hydroxide molybdotungstate compositions are further characterized by their x-ray powder diffraction pattern as shown in Table A above and FIG. 1.
  • the crystalline transition metal oxy-hydroxide molybdotungstate composition may have a binder incorporated, where the selection of binder includes but is not limited to, anionic and cationic clays such as hydrotal cites, 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.
  • anionic and cationic clays such as hydrotal cites, pyroaurite-sjogrenite- hydrotalcites, montmorillonite and related clays, kaolin, sepiolites, silicas
  • binders may be applied with or without peptization.
  • the binder may be added to the bulk crystalline transition metal oxy-hydroxide molybdotungstate composition, and the amount of binder may range from 1 to 30 wt% of the finished catalysts or from 5 to 26 wt% of the finished catalyst.
  • the binder may be chemically bound to the crystalline transition metal oxy-hydroxide molybdotungstate composition, or may be present in a physical mixture with the crystalline transition metal oxy-hydroxide molybdotungstate composition.
  • the crystalline transition metal oxy-hydroxide molybdotungstate composition 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 crystalline transition metal oxy- hydroxide molybdotungstate composition with a sulfur containing feed as well as the use of a gaseous mixture of H2S / H2.
  • the sulfidation of the crystalline transition metal oxy-hydroxide molybdotungstate composition 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 unsupported crystalline transition metal oxy-hydroxide molybdotungstate material 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 transition metal oxy-hydroxide molybdate material is useful as a catalyst. Examples of specific hydroprocessing processes are well known in the art and include hydrodenitrification, hydrodesulfurization, hydrodemetallation,
  • hydrodesilication hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking
  • the operating conditions of the hydroprocessing processes listed above typically include reaction pressures from 2.5 MPa to 17.2 MPa, or in the range of 5.5 to 17.2 MPa, with reaction temperatures in the range of 245°C to 440°C, or in the range of 285°C to
  • 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 0.1 h “1 to 10 h “1 , or 2.0 h “1 to 8.0 h “1 .
  • operating conditions may include from 3.5 MPa to 8.6 MPa, from 315°C to 410°C, from 0.25/h to 5/h, and from 84 Nm 3 H 2 /m 3 to 850 Nm 3 H 2 /m 3 feed.
  • Other feedstocks may include gasoline, naphtha, kerosene, gas oils, distillates, and reformate.
  • 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.
  • the purity of a synthesized product may be assessed with reference to its x-ray powder diffraction pattern.
  • a sample is stated to be pure, it is intended only that the x-ray powder diffraction pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
  • different poorly crystalline materials 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.
  • Embodiment 1 is a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
  • Embodiment 2 is a method of making a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula: ( H 4 )AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be ⁇ 1.501, or ⁇ 1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in
  • the method comprising: (a) forming a reaction mixture containing NH 3 , H2O, and sources of M, W, and Mo; (b) adjusting the pH of the reaction mixture to a pH of from 8.5 to 10; (c) reacting the reaction mixture between 100°C and 220°C in an autogenous environment, and (d) recovering the crystalline transition metal oxy-hydroxide molybdotungstate material.
  • the method of embodiment 2 further comprising adding a binder to the recovered crystalline transition metal oxy-hydroxide molybdotungstate material wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.
  • 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 crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
  • ( H 4 )AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be ⁇ 1.501, or ⁇ 1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

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Abstract

A hydroprocessing catalyst has been developed. The catalyst is a unique crystalline transition metal oxy-hydroxide molybdotungstate material. The hydroprocessing using the crystalline ammonia transition metal oxy-hydroxide molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

Description

CRYSTALLINE TRANSITION METAL OXY-HYDROXIDE MOLYBDOTUNGSTATE
PRIORITY CLAIM OF EARLIER NATIONAL APPLICATION
[0001] This application claims priority to U.S. Application No. 62/267,870 filed
December 15, 2015, the contents of which are hereby incorporated by reference. FIELD OF THE INVENTION
[0002] This invention relates to a new hydroprocessing catalyst. More particularly this invention relates to a unique crystalline transition metal oxy-hydroxide molybdotungstate and its use as a hydroprocessing catalyst. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.
BACKGROUND
[0003] In order to meet the growing demand for petroleum products there is greater utilization of sour crudes, which when combined with tighter environmental legislation regarding the concentration of nitrogen and sulfur within fuel, leads to accentuated refining problems. The removal of sulfur (hydrodesulfurization - HDS) and nitrogen
(hydrodenitrification - HDN) containing compounds from fuel feed stocks is targeted during the hydrotreating steps of refining and is achieved by the conversion of organic nitrogen and sulfur to ammonia and hydrogen sulfide respectively.
[0004] Since the late 1940s the use of catalysts containing nickel (Ni) and molybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfur removal. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad, Division of Petroleum Chemistry, 115th Meeting ACS, San Francisco, 1949. For several decades now there has been an intense interest directed towards the development of materials to catalyze the deep desulfurization, in order to reduce the sulfur concentration to the ppm level. Some recent breakthroughs have focused on the development and application of more active and stable catalysts targeting the production of feeds for ultra low sulfur fuels. Several studies have demonstrated improved HDS and HDN activities through elimination of the support such as, for example, AI2O3. Using bulk unsupported materials provides a route to increase the active phase loading in the reactor as well as providing alternative chemistry to target these catalysts.
[0005] More recent research in this area has focused on the ultra deep desulfurization properties achieved by a Ni-Mo/W unsupported 'trimetallic' material reported in, for example, US 6, 156,695. The controlled synthesis of a broadly amorphous mixed metal oxide consisting of molybdenum, tungsten and nickel, significantly outperformed conventional hydrotreating catalysts. The structural chemistry of the tri-metallic mixed metal oxide material was likened to the hydrotalcite family of materials, referring to literature articles detailing the synthesis and characterization of a layered nickel molybdate material, stating that the partial substitution of molybdenum with tungsten leads to the production of a broadly amorphous phase which, upon decomposition by sulfidation, gives rise to superior hydrotreating activities.
[0006] The chemistry of these layered hydrotalcite-like materials was first reported by H. Pezerat, contribution a Γ etude des molybdates hydrates de zinc, cobalt et nickel, C. R. Acad. Sci., 261, 5490, who identified a series of phases having ideal formulas MM0O4.H2O,
ΕΗΜ2θ-(Μοθ4)2.Η20, and Ε2 (Η3θ Μ20(Μοθ4)2 where E can be H4 +, Na+ or K+ and M can be Zn2+, Co2+ or Ni2+.
[0007] Pezerat assigned the different phases he observed as being < c, Oy or Oy and determined the crystal structures for Φχ and Oy, however owing to a combination of the small crystallite size, limited crystallographic capabilities and complex nature of the material, there were doubts raised as to the quality of the structural assessment of the materials. During the mid 1970s, Clearfield et al attempted a more detailed analysis of the Φχ and Oy phases, see examples A. Clearfield, M. J. Sims, R. Gopal, Inorg. Chem., 75, 335; A. Clearfield, R. Gopal, C. H. Saldarriaga-Molina, Inorg. Chem., 16, 628. Single crystal studies on the product from a hydrothermal approach allowed confirmation of the Φχ structure, however they failed in their attempts to synthesize Oy and instead synthesized an alternative phase, Na- Cu(OH)(Mo04), see A. Clearfield, A. Moini, P. R. Rudolf, Inorg. Chem., 24, 4606.
[0008] The structure of Oy was not confirmed until 1996 when by Ying et al. Their investigation into a room temperature chimie douce synthesis technique in the pursuit of a layered ammonium zinc molybdate led to a metastable aluminum-substituted zincite phase, prepared by the calcination of Zn/Al layered double hydroxide (Zn4Al2(OH)i2C03 zH20). See example D. Levin, S. L. Soled, J. Y. Ying, Inorg. Chem., 1996, 35, 4191-4197. This material was reacted with a solution of ammonium heptamolybdate at room temperature to produce a highly crystalline compound, the structure of which could not be determined through conventional ab-initio methods. The material was indexed, yielding crystallographic parameters which were the same as that of an ammonium nickel molybdate, reported by Astier, see example M. P. Astier, G. Dji, S. Teichner, J. Ann. Chim. (Paris), 1987, 12, 337, a material belonging to a family of ammonium-amine-nickel-molybdenum oxides closely related to Pezerat's materials. Astier did not publish any detailed structural data on this family of materials, leading to Ying et al reproducing the material to be analyzed by high resolution powder diffraction in order to elucidate the structure. Ying et al named this class of materials 'layered transition-metal molybdates' or LTMs.
SUMMARY OF THE INVENTION
[0009] A unique crystalline transition metal oxy-hydroxide molybdotungstate material has been produced and optionally sulfided, to yield an active hydroprocessing catalyst. The crystalline transition metal oxy-hydroxide molybdotungstate material has a unique x-ray powder diffraction pattern showing strong peaks at 9.65, 7.3 and 5.17A. The crystalline transition metal oxy-hydroxide molybdotungstate material has the formula:
(NH4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from
0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000005_0001
[0010] Another embodiment involves a method of making a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
( H4)AM(OH)BMOXWYOZ
where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A: TABLE A
Figure imgf000006_0001
the method comprising forming a reaction mixture containing H3, H2O, and sources of M, W, and Mo; adjusting the pH of the reaction mixture to a pH of from 8.5 to 10; reacting the mixture together at elevated temperature with an autogenous pressure and then recovering the crystalline transition metal oxy-hydroxide molybdotungstate material. The reacting may be conducted at a temperature of from 70°C to 200°C for a period of time from 30 minutes to 14 days.
[0011] Yet another embodiment involves a conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising: a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000007_0001
[0012] Additional features and advantages of the invention will be apparent from the description of the invention, the drawing and claims provided herein.
BRIEF DESCRIPTION OF THE DRAWING
[0013] FIG. 1 is the x-ray powder diffraction pattern of a crystalline transition metal oxy-hydroxide molybdotungstate prepared by boiling crystallization as described in Examples 1 to 3.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The present invention relates to a crystalline transition metal oxy-hydroxide molybdotungstate material and a process for preparing the material. The material has the designation UPM-9. The crystalline transition metal oxy-hydroxide molybdotungstate material has an empirical formula: ( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y.
[0015] The crystalline composition of the invention is characterized by having an extended network of M-O-M, 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.
[0016] The crystalline transition metal oxy -hydroxide molybdotungstate composition having an x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A.
TABLE A
Figure imgf000008_0001
[0017] The crystalline transition metal oxy-hydroxide molybdotungstate composition of the invention having the x-ray powder diffraction pattern shown in FIG. 1. [0018] The crystalline transition metal oxy-hydroxide molybdotungstate composition is prepared by solvothermal crystallization of a reaction mixture typically prepared by mixing reactive sources of molybdenum and tungsten 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, 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.
[0019] 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.
[0020] Generally, the solvothermal process used to prepare the composition of this invention involves forming a reaction mixture wherein all of the components, such as for example, Ni, Mo, H3 and H2O 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:
AMOx : BMOOY : CWOz: D( H3) : H2O 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 varies from 0.1 to 3 or from 0.5 to 2 or from 0.75 to 1.25; 'x' is a number which satisfies the valency of 'M'; 'B' represents the molar ratio of 'Mo' and varies from 0.1 to 3 or from 0.5 to 2 or from 0.75 to 1.25; 'y' is a number satisfies the valency of 'Mo'; 'B' represents the molar ratio of 'W and varies from 0.01 to 1 or from 0.05 to 0.8 or from 0.1 to 0.6; 'D' represents the molar ratio of H3 and varies from 0.01 to 50 or from 0.1 to 40 or from 1 to 30 ; the molar ratio of H2O and varies from 10 to 1000 or from 50 to 500 or from 90 to 300. [0021] The pH of the mixture is adjusted to a value ranging from 7.5 to 11, or from 8.5 to 10. The pH of the mixture can be controlled through the addition of a base such as Η4ΟΗ, quaternary ammonium hydroxides, amines, and the like.
[0022] Once the reaction mixture is formed, the reaction mixture is reacted at temperatures ranging from 70°C to 230°C for a period of time ranging from 30 minutes to around 14 days. In one embodiment the temperate range for the reaction is from 110°C to 120°C and in another embodiment the temperature is in the range of from 150°C to 180°C. In one embodiment, the reaction time is from 4 to 6 hours, and in another embodiment the reaction time is from 7 to 10 days. 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 crystalline transition metal oxy- hydroxide molybdotungstate compositions are recovered as the reaction product. The crystalline transition metal oxy-hydroxide molybdotungstate compositions are further characterized by their x-ray powder diffraction pattern as shown in Table A above and FIG. 1.
[0023] Once formed, the crystalline transition metal oxy-hydroxide molybdotungstate composition may have a binder incorporated, where the selection of binder includes but is not limited to, anionic and cationic clays such as hydrotal cites, 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 transition metal oxy-hydroxide molybdotungstate composition, and the amount of binder may range from 1 to 30 wt% of the finished catalysts or from 5 to 26 wt% of the finished catalyst. The binder may be chemically bound to the crystalline transition metal oxy-hydroxide molybdotungstate composition, or may be present in a physical mixture with the crystalline transition metal oxy-hydroxide molybdotungstate composition.
[0024] The crystalline transition metal oxy-hydroxide molybdotungstate composition, 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 crystalline transition metal oxy- hydroxide molybdotungstate composition with a sulfur containing feed as well as the use of a gaseous mixture of H2S / H2. The sulfidation of the crystalline transition metal oxy-hydroxide molybdotungstate composition is performed at elevated temperatures, typically ranging from 50 to 600°C, or from 150 to 500°C, or from 250 to 450°C.
[0025] The unsupported crystalline transition metal oxy-hydroxide molybdotungstate material 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 transition metal oxy-hydroxide 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
[0026] The operating conditions of the hydroprocessing processes listed above typically include reaction pressures from 2.5 MPa to 17.2 MPa, or in the range of 5.5 to 17.2 MPa, with reaction temperatures in the range of 245°C to 440°C, or in the range of 285°C to
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 0.1 h"1 to 10 h"1, or 2.0 h"1 to 8.0 h"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 3.5 MPa to 8.6 MPa, from 315°C to 410°C, from 0.25/h to 5/h, and from 84 Nm3 H2/m3 to 850 Nm3 H2/m3 feed. Other feedstocks may include gasoline, naphtha, kerosene, gas oils, distillates, and reformate.
[0027] 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.
[0028] 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° (2Θ). Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as Θ, where Θ is the Bragg angle as observed from digitized data. Intensities were determined from the integrated area of diffraction peaks after subtracting background, "Io" 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 2Θ is subject to both human and mechanical error, which in combination can impose an uncertainty of ±0.4° on each reported value of 2Θ. This uncertainty is also translated to the reported values of the d-spacings, which are calculated from the 2Θ values. In some of the x-ray powder diffraction 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/Io), the above designations are defined as: W=0-15, M=15-60: S=60-80 AND VS=80-100
[0029] 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 powder diffraction 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 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
[0030] In a 2 liter flask, 125.71g of nickel nitrate hexahydrate (0.43 moles of Ni), 23.2g of molybdenum trioxide (0.16 moles of Mo) and 77g of ammonium metatungstate (0.31 moles of W) were dissolved in 1200ml of water. The pH of the solution was increased to 9 using concentrated NH4OH (300ml). At this point the solution was transferred to a 2-liter stainless steel autoclave, the heat was ramped to 180°C over a period of 2 hours and held at 180°C for 24 hours, after which time the autoclave was cooled to room temperature, filtered, washed with 90 ml of 90°C water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectra shown in FIG. 1. EXAMPLE 2
[0031] In a 2 liter flask, 104.76g of nickel nitrate hexahydrate (0.36 moles of Ni), 126.96g of ammonium heptamolybdate (0.72 moles of Mo) and 53.28g of ammonium metatungstate (0.21 moles of W) were dissolved in 1008ml of water. The pH of the solution was increased to 9 using concentrated H4OH (100ml). At this point the solution was transferred to a 2-liter stainless steel autoclave, the heat was ramped to 180°C over a period of 2 hours and held at 180°C for 24 hours, after which time the autoclave was cooled to room temperature, filtered, washed with 90 ml of 90°C water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectra shown in FIG. 1.
EXAMPLE 3
[0032] In a 2 liter flask, 104.76g of nickel nitrate hexahydrate (0.36 moles of Ni), 95.22g of ammonium heptamolybdate (0.54 moles of Mo) and 53.28g of ammonium metatungstate (0.21 moles of W) were dissolved in 1008ml of water. The pH of the solution was increased to 9 using concentrated NH4OH (100ml). At this point the solution was transferred to a 2-liter stainless steel autoclave, the heat was ramped to 180°C over a period of 2 hours and held at 150°C for 7 days, after which time the autoclave was cooled to room temperature, filtered, washed with 90 ml of 90°C water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectra shown in FIG. 1.
EMBODIMENTS
[0033] Embodiment 1 is a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
(NH4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A: TABLE A
Figure imgf000014_0001
[0034] The crystalline transition metal oxy-hydroxide molybdotungstate material of embodiment 1 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt% binder.
[0035] The crystalline transition metal oxy-hydroxide molybdotungstate material of embodiment 1 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material 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.
[0036] The crystalline transition metal oxy-hydroxide molybdotungstate material of embodiment 1 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material is sulfided.
[0037] Embodiment 2 is a method of making a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula: ( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000015_0001
the method comprising: (a) forming a reaction mixture containing NH3, H2O, and sources of M, W, and Mo; (b) adjusting the pH of the reaction mixture to a pH of from 8.5 to 10; (c) reacting the reaction mixture between 100°C and 220°C in an autogenous environment, and (d) recovering the crystalline transition metal oxy-hydroxide molybdotungstate material.
[0038] The method of embodiment 2 wherein the reacting is conducted at a temperature of from 100°C to 200°C for a period of time from 30 minutes to 14 days.
[0039] The method of embodiment 2 wherein the recovering is by filtration or centrifugation. [0040] The method of embodiment 2 further comprising adding a binder to the recovered crystalline transition metal oxy-hydroxide molybdotungstate material.
[0041] The method of embodiment 2 further comprising adding a binder to the recovered crystalline transition metal oxy-hydroxide molybdotungstate material wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.
[0042] The method of embodiment 2 further comprising sulfiding the recovered crystalline transition metal oxy-hydroxide molybdotungstate material.
[0043] 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 crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0; 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5, or from 0.75 to 1.5, or from 0.8 to 1.2; 'y' varies from 0.01 to 0.4, or from 0.01 to 0.25; where the sum of (x+y) must be < 1.501, or <1.2 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000017_0001
[0044] The process of embodiment 3 wherein the conversion process is hydroprocessing.
[0045] The process of embodiment 3 wherein the conversion process is selected from the group consisting of hydrodemtrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.
[0046] The process of embodiment 3 wherein the crystalline transition metal oxy- hydroxide molybdotungstate material is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt% binder.
[0047] The process of embodiment 3 wherein the crystalline transition metal oxy- hydroxide molybdotungstate material is sulfided.

Claims

CLAIMS:
1. A crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5; 'y' varies from 0.01 to 0.4; where the sum of (x+y) must be < 1.501; 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000018_0001
2. The crystalline transition metal oxy-hydroxide molybdotungstate material of claim 1 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material is present in a mixture with at least one binder selected from the group consisting of silicas, aluminas, and silica-aluminas and wherein the mixture comprises up to 25 wt% binder.
3. The crystalline transition metal oxy -hydroxide molybdotungstate material of claim 1 wherein the crystalline transition metal oxy -hydroxide molybdotungstate material is sulfided.
4. A method of making a crystalline transition metal oxy-hydroxide
molybdotungstate material having the formula:
( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5; 'y' varies from 0.01 to 0.4; where the sum of (x+y) must be < 1.501; 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000019_0001
the method comprising:
(a) forming a reaction mixture containing NH3, H2O, and sources of M, W, and Mo; (b) adjusting the pH of the reaction mixture to a pH of from 8.5 to 10; (c) reacting the reaction mixture between 100°C and 220°C in an autogenous environment; and
(d) recovering the crystalline transition metal oxy -hydroxide molybdotungstate
material.
5. The method of claim 4 wherein the reacting is conducted at a temperature of from 10°C to 200°C for a period of time from 30 minutes to 14 days.
6. The method of claim 4 further comprising adding a binder selected from the group consisting of aluminas, silicas, and alumina-silicas to the recovered crystalline transition metal oxy-hydroxide molybdotungstate material.
7. The method of claim 4 further comprising sulfiding the recovered crystalline transition metal oxy-hydroxide molybdotungstate material.
8. A conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising: a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
( H4)AM(OH)BMOXWYOZ where "a" varies from 0.1 to 10, 'M' is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; 'b' varies from 0.1 to 2; 'x' varies from 0.5 to 1.5; 'y' varies from 0.01 to 0.4; where the sum of (x+y) must be < 1.501; 'z' is a number which satisfies the sum of the valency of a, M, b, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE A
Figure imgf000021_0001
9. The process of claim 8 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt% binder.
10. The process of claim 8 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material is sulfided.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109518274A (en) * 2019-01-07 2019-03-26 合肥学院 Dodecatungstate crystal material with two-dimensional nano-pore cavity structure and preparation method thereof

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10449523B2 (en) * 2015-12-15 2019-10-22 Uop Llc Crystalline bis-ammonia transition metal molybdotungstate
US10882030B2 (en) 2017-08-25 2021-01-05 Uop Llc Crystalline transition metal tungstate
US10773245B2 (en) 2017-08-25 2020-09-15 Uop Llc Crystalline transition metal molybdotungstate
US10875013B2 (en) 2017-12-20 2020-12-29 Uop Llc Crystalline oxy-hydroxide transition metal molybdotungstate
US10995013B2 (en) 2017-12-20 2021-05-04 Uop Llc Mixed transition metal tungstate
US11007515B2 (en) 2017-12-20 2021-05-18 Uop Llc Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds
US11117811B2 (en) 2017-12-20 2021-09-14 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US11078088B2 (en) 2017-12-20 2021-08-03 Uop Llc Highly active multimetallic materials using short-chain alkyl quaternary ammonium compounds
US10843176B2 (en) 2017-12-20 2020-11-24 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US10822247B2 (en) 2017-12-20 2020-11-03 Uop Llc Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds
US11034591B2 (en) 2017-12-20 2021-06-15 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US11033883B2 (en) * 2018-06-26 2021-06-15 Uop Llc Transition metal molybdotungstate material
US10737249B2 (en) 2018-06-26 2020-08-11 Uop Llc Crystalline transition metal molybdotungstate
US10688479B2 (en) * 2018-06-26 2020-06-23 Uop Llc Crystalline transition metal tungstate
US10682632B2 (en) 2018-06-26 2020-06-16 Uop Llc Transition metal tungstate material
US10737248B2 (en) * 2018-06-26 2020-08-11 Uop Llc Crystalline transition metal tungstate
US10737246B2 (en) 2018-06-29 2020-08-11 Uop Llc Poorly crystalline transition metal tungstate
US10981151B2 (en) * 2018-06-29 2021-04-20 Uop Llc Poorly crystalline transition metal molybdotungstate
KR102508792B1 (en) 2018-08-07 2023-03-13 엘지디스플레이 주식회사 Display device
US11213803B2 (en) 2018-12-13 2022-01-04 Uop Llc Ammonia-free synthesis for Al or Si based multimetallic materials
US10933407B2 (en) 2018-12-13 2021-03-02 Uop Llc Ammonia-free synthesis for Al or Si based multimetallic materials
US11426711B2 (en) * 2019-05-22 2022-08-30 Uop Llc Method of making highly active metal oxide and metal sulfide materials
CN116917038A (en) * 2021-02-16 2023-10-20 雪佛龙美国公司 Multimetal bulk hydroprocessing catalyst
US11707733B2 (en) * 2021-02-22 2023-07-25 Chevron U.S.A. Inc. Multi-metallic bulk hydroprocessing catalysts

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678124A (en) * 1968-10-24 1972-07-18 Gennady Arkadievich Stepanov Process for the production of mono- and diolefin hydrocarbons
US6156695A (en) * 1997-07-15 2000-12-05 Exxon Research And Engineering Company Nickel molybdotungstate hydrotreating catalysts

Family Cites Families (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820677A (en) 1984-04-02 1989-04-11 Jacobson Allan J Amorphous, iron promoted Mo and W sulfide hydroprocessing catalysts and process for their preparation
US4904634A (en) 1986-12-29 1990-02-27 Aluminum Company Of America Active material useful as adsorbent comprising metal oxide/hydroxide surfaces reacted with one or more phosphorous-containing materials having selected organic radicals attached thereto
US5278121A (en) 1990-10-01 1994-01-11 Exxon Research & Engineering Company Multimetallic sulfide catalyst containing noble metals for hydrodenitrogenation
JP3802106B2 (en) 1995-06-08 2006-07-26 日本ケッチェン株式会社 Hydrocarbon oil hydrotreating catalyst, production method thereof and activation method thereof
RU2098181C1 (en) 1996-04-23 1997-12-10 Завод по производству катализаторов Акционерного общества "Куйбышевнефтеоргсинтез" Method of preparing catalyst for hydrofining of petroleum fractions
US7513989B1 (en) 1997-07-15 2009-04-07 Exxonmobil Research And Engineering Company Hydrocracking process using bulk group VIII/Group VIB catalysts
US6162350A (en) 1997-07-15 2000-12-19 Exxon Research And Engineering Company Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901)
US6635599B1 (en) 1997-07-15 2003-10-21 Exxonmobil Research & Engineering Company Mixed metal catalyst, its preparation by co-precipitation, and its use
US6783663B1 (en) 1997-07-15 2004-08-31 Exxonmobil Research And Engineering Company Hydrotreating using bulk multimetallic catalysts
US6712955B1 (en) 1997-07-15 2004-03-30 Exxonmobil Research And Engineering Company Slurry hydroprocessing using bulk multimetallic catalysts
US6863803B1 (en) 1997-07-15 2005-03-08 Exxonmobil Research And Engineering Company Production of low sulfur/low nitrogen hydrocrackates
US6758963B1 (en) * 1997-07-15 2004-07-06 Exxonmobil Research And Engineering Company Hydroprocessing using bulk group VIII/group vib catalysts
US7229548B2 (en) 1997-07-15 2007-06-12 Exxonmobil Research And Engineering Company Process for upgrading naphtha
US7232515B1 (en) 1997-07-15 2007-06-19 Exxonmobil Research And Engineering Company Hydrofining process using bulk group VIII/Group VIB catalysts
US7288182B1 (en) 1997-07-15 2007-10-30 Exxonmobil Research And Engineering Company Hydroprocessing using bulk Group VIII/Group VIB catalysts
US6929738B1 (en) 1997-07-15 2005-08-16 Exxonmobil Research And Engineering Company Two stage process for hydrodesulfurizing distillates using bulk multimetallic catalyst
US6620313B1 (en) 1997-07-15 2003-09-16 Exxonmobil Research And Engineering Company Hydroconversion process using bulk group VIII/Group VIB catalysts
US6582590B1 (en) 1997-07-15 2003-06-24 Exxonmobil Research And Engineering Company Multistage hydroprocessing using bulk multimetallic catalyst
JP4174887B2 (en) 1998-05-21 2008-11-05 堺化学工業株式会社 Method for producing fine spherical particles of nickel, cobalt or copper carbonate or hydroxide
US6534437B2 (en) 1999-01-15 2003-03-18 Akzo Nobel N.V. Process for preparing a mixed metal catalyst composition
US6299760B1 (en) 1999-08-12 2001-10-09 Exxon Research And Engineering Company Nickel molybodtungstate hydrotreating catalysts (law444)
US7557062B2 (en) * 2003-02-24 2009-07-07 Shell Oil Company Catalyst composition, its preparation and use
AR043242A1 (en) 2003-02-24 2005-07-20 Shell Int Research PREPARATION AND USE OF A CATALYST COMPOSITION
US7232934B2 (en) 2003-09-19 2007-06-19 Exxonmobil Chemical Patents Inc. Hydrogenation of oxo aldehydes to oxo alcohols in the presence of a nickel-molybdenum catalyst
US7776205B2 (en) 2004-04-22 2010-08-17 Exxonmobil Research And Engineering Company Process to upgrade hydrocarbonaceous feedstreams
US7709412B2 (en) 2004-04-22 2010-05-04 Exxonmobil Research & Engineering Company Bulk metal hydrotreating catalyst used in the production of low sulfur diesel fuels
DK1737933T3 (en) 2004-04-22 2016-01-11 Albemarle Netherlands Bv Hydrogen treatment catalyst containing a group v metal
US7691257B2 (en) 2004-04-22 2010-04-06 Exxonmobil Research And Engineering Company Process to manufacture low sulfur diesel fuels
US7780845B2 (en) 2004-04-22 2010-08-24 Exxonmobil Research And Engineering Company Process to manufacture low sulfur distillates
US7648941B2 (en) 2004-09-22 2010-01-19 Exxonmobil Research And Engineering Company Bulk bimetallic catalysts, method of making bulk bimetallic catalysts and hydroprocessing using bulk bimetallic catalysts
US7544632B2 (en) 2004-09-22 2009-06-09 Exxonmobil Research And Engineering Company Bulk Ni-Mo-W catalysts made from precursors containing an organic agent
US7591942B2 (en) 2004-09-22 2009-09-22 Exxonmobil Research And Engineering Company Bulk bi-metallic catalysts made from precursors containing an organic agent
MXPA05009283A (en) * 2005-08-31 2007-02-27 Mexicano Inst Petrol PROCEDURE FOR THE PREPARATION OF A CATALYTIC COMPOSITION FOR THE HYDROPROCESSING OF PETROLEUM FRACTIONS.
US7605107B2 (en) 2005-09-29 2009-10-20 Exxonmobil Research And Engineering Company Method of preparing a supported hydrotreating catalyst
US7538066B2 (en) 2005-09-29 2009-05-26 Exxonmobil Research And Engineering Company Method of preparing a hydrotreating catalyst on a support containing a rare earth metal
WO2007050636A2 (en) 2005-10-26 2007-05-03 Exxonmobil Research And Engineering Company Hydroprocessing using bulk bimetallic catalysts
CA2626139C (en) * 2005-10-26 2012-07-03 Exxonmobil Research And Engineering Company Hydroprocessing using hydrothermally-prepared bulk multimetallic catalysts
CN101365538B (en) 2005-10-26 2013-02-13 雅宝荷兰有限责任公司 A bulk catalyst comprising nickel tungsten metal oxidic particles
KR101353807B1 (en) * 2005-10-26 2014-01-21 알베마를 네덜란드 비.브이. A bulk catalyst comprising metal oxidic particles of group vi and viii and a process for the manufacture therof
US8216958B2 (en) 2006-01-17 2012-07-10 Exxonmobil Research And Engineering Company Selective catalysts having silica supports for naphtha hydrodesulfurization
US7951746B2 (en) 2006-10-11 2011-05-31 Exxonmobil Research And Engineering Company Bulk group VIII/group VIB metal catalysts and method of preparing same
FR2910351B1 (en) 2006-12-22 2009-02-27 Total France Sa HYDROTREATING CATALYST, PROCESS FOR PREPARING THE SAME AND USE THEREOF
US20090114566A1 (en) 2007-10-31 2009-05-07 Chevron U.S.A. Inc. Method of upgrading heavy hydrocarbon streams to jet products
US8173570B2 (en) 2007-10-31 2012-05-08 Chevron U.S.A. Inc. Hydroconversion processes employing multi-metallic catalysts and method for making thereof
EP2217373B1 (en) 2007-11-09 2019-03-06 ExxonMobil Research and Engineering Company Preparation of bulk metallic group viii/group vib metal catalysts
US9708548B2 (en) 2007-12-04 2017-07-18 Exxonmobil Research And Engineering Company Hydrocarbon hydroprocessing using bulk catalyst composition
WO2009073785A1 (en) 2007-12-04 2009-06-11 Albemarle Netherlands, B.V. Bulk catalyst composition comprising bulk metal oxide particles
EP2103347A1 (en) 2008-03-17 2009-09-23 ExxonMobil Research and Engineering Company Hydrocarbon hydroprocessing using bulk catalyst composition
CN101544904B (en) 2008-03-28 2012-11-14 中国科学院大连化学物理研究所 Composite metal oxide catalyst, preparation and application thereof
TW200950880A (en) 2008-04-09 2009-12-16 Basf Se Coated catalysts comprising a multimetal oxide comprising molybdenum, bismuth and iron
CN101439882B (en) * 2008-12-17 2010-09-01 中国石油天然气集团公司 Method for synthesizing mesoporous ammonium nickel molybdate by using urea as precipitating agent
US8058203B2 (en) * 2009-04-29 2011-11-15 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
EP2424663B1 (en) * 2009-04-29 2019-05-22 Chevron U.S.A., Inc. Method for making a hydroconversion multi-metallic catalyst
US8383543B2 (en) 2009-04-29 2013-02-26 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US8080492B2 (en) 2009-04-29 2011-12-20 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
CN102049265B (en) 2009-10-27 2013-01-09 中国石油化工股份有限公司 Hydrotreating catalyst and preparation method thereof
CN102906231B (en) * 2009-12-08 2015-11-25 埃克森美孚研究工程公司 Use the method for body catalyst hydrotreatment height nitrogen charging
US8636967B2 (en) 2010-01-21 2014-01-28 Intevep, S.A. Metal recovery from hydroconverted heavy effluent
US8586500B2 (en) 2010-11-11 2013-11-19 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US8703641B2 (en) 2010-11-11 2014-04-22 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US8658558B2 (en) 2010-11-11 2014-02-25 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
WO2012092006A2 (en) 2010-12-30 2012-07-05 Chevron U.S.A. Inc. Hydroprocessing catalysts and methods for making thereof
US10507458B2 (en) 2012-08-29 2019-12-17 Indian Oil Corporation Limited Hydrotreating catalyst and process for preparing the same
US9435043B2 (en) 2014-04-14 2016-09-06 California Institute Of Technology Oxygen evolution reaction catalysis
US10046315B2 (en) 2015-12-15 2018-08-14 Uop Llc Crystalline transition metal molybdotungstate
US10053637B2 (en) 2015-12-15 2018-08-21 Uop Llc Transition metal tungsten oxy-hydroxide
US10399063B2 (en) 2015-12-15 2019-09-03 Uop Llc Mixed metal oxides
US10052616B2 (en) 2015-12-15 2018-08-21 Uop Llc Crystalline ammonia transition metal molybdotungstate
US10399065B2 (en) 2015-12-15 2019-09-03 Uop Llc Crystalline transition metal tungstate
US10005812B2 (en) 2015-12-15 2018-06-26 Uop Llc Transition metal molybdotungsten oxy-hydroxide
US10052614B2 (en) 2015-12-15 2018-08-21 Uop Llc Mixed metal oxides
US10232357B2 (en) 2015-12-15 2019-03-19 Uop Llc Crystalline ammonia transition metal molybdate
EP3408023B1 (en) 2016-01-29 2024-03-20 TotalEnergies OneTech Homogeneously dispersed multimetal oxy-hydroxide catalysts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678124A (en) * 1968-10-24 1972-07-18 Gennady Arkadievich Stepanov Process for the production of mono- and diolefin hydrocarbons
US6156695A (en) * 1997-07-15 2000-12-05 Exxon Research And Engineering Company Nickel molybdotungstate hydrotreating catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3390282A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109518274A (en) * 2019-01-07 2019-03-26 合肥学院 Dodecatungstate crystal material with two-dimensional nano-pore cavity structure and preparation method thereof

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