Crystalline multinary metal oxide compositions, process for preparing and processes for using the composition

• US 6,171,571 B1
• Filed: 05/10/1999
• Issued: 01/09/2001
• Est. Priority Date: 05/10/1999
• Status: Expired due to Term

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Koster, Susan C., Bogdan, Paula L., Bedard, Robert L., King, Lisa M.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): SAMPLE, DAVID R
• Application Number:
  US09/309,040
• Time in Patent Office: 610 Days
• Field of Search: 423/508, 423/593, 423/606, 423/641, 501/134, 502/215, 502/311, 502/312, 502/317, 502/353, 558/321, 558/322, 558/323, 558/325
• US Class Current: 423/594.7
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/04 Alkali metals
• CPC Class Codes: B01J 23/20 Vanadium, niobium or tantalum
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/11 Lithium
• CPC Class Codes: B01J 2523/55 Vanadium
• CPC Class Codes: B01J 2523/56 Niobium
• CPC Class Codes: B01J 2523/68 Molybdenum
• CPC Class Codes: B01J 2523/69 Tungsten
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/10 in the presence of water, e.g. steam
• CPC Class Codes: C01G 33/006 Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01G 39/006 Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01G 41/006 Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/80 : Compositional purity
• CPC Class Codes: C01P 2006/82 : water content
• CPC Class Codes: C07C 253/24 : by ammoxidation of hydrocarbons or substituted hydrocarbons
• CPC Class Codes: C07C 255/08 : Acrylonitrile; Methacrylonitrile
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

A new family of crystalline metal oxide compositions have been synthesized. These compositions are described by the empirical formula:

A_nNbM_xM′_yM″_mO_p

where A is an alkali metal cation, ammonium ion and mixtures thereof, M is tungsten, molybdenum, or mixtures thereof. M′ is vanadium, tantalum and mixtures thereof, and M″ is antimony, tellurium and mixtures thereof. M′ and M″ are optional metals. These compositions are characterized by having an x-ray diffraction pattern having at least one peak at a d spacing of about 3.9 Å. A hydrothermal synthesis procedure as well as processes using the composition, e.g., ammoxidation of propane, are also disclosed.

Claims

1. A crystalline metal oxide composition having an empirical formula of:

2. The composition of claim 1 where A is lithium.

3. The composition of claim 1 where M is molybdenum.

4. The composition of claim 1 where M is molybdenum, M′

is vanadium and M″

is antimony.

5. The composition of claim 1 further characterized in that the A cation has been exchanged for a secondary cation selected from the group consisting of hydronium ions, alkali ions, alkaline earth ions, lanthanide ions, divalent transition metal ions, trivalent transition metal ions, organic cations and mixtures thereof.

6. A crystalline metal oxide composition having an empirical formula of:

7. The composition of claim 6 where A is lithium.

8. The composition of claim 6 where M is molybdenum.

9. The composition of claim 6 further characterized in that the A cation has been exchanged for a secondary cation selected from the group consisting of hydronium ions, alkali ions, alkaline earth ions, lanthanide ions, divalent transition metal ions, trivalent transition metal ions, organic cations and mixtures thereof.

10. A process for preparing a crystalline metal oxide composition having an empirical formula of:

11. The process of claim 10 where the temperature varies from about 100°

C. to about 225°

C. and the time varies from about 1 hour to about 96 hours.

12. The process of claim 10 where the alkaline metal source is selected from the group consisting of halide, acetate, hydroxide and carbonate compounds of the alkali metals.

13. The process of claim 10 where the niobium source is selected from the group consisting of niobium oxide, hydrous niobium oxide, niobium ethoxide, and ammonium niobium oxalate.

14. The process of claim 10 where the vanadium source is selected from the group consisting of vanadium (V) oxide, vanadium (V) oxychloride, vanadium oxide sulfate, and ammonium vanadate.

15. The process of claim 10 where the molybdenum source is selected from the group consisting of molybdic acid ((NH₄)₆Mo₇O₂₄.4H₂O), molybdenum trioxide (MoO₃), sodium molybdate, and molybdenum (VI) oxychloride.

16. The process of claim 10 where the W source is selected from the group consisting of ammonium tungstate, tungsten (VI) oxide, tungsten (VI) chloride, sodium tungstate, and tungstic acid.

17. The process of claim 10 further characterized in that the A cation is exchanged for a secondary cation selected from the group consisting of hydronium ions, alkali ions, alkaline earth ions, lanthanide ions, divalent transition metal ions, trivalent transition metal ions, organic cations and mixtures thereof by contacting the composition with solution containing at least one of said secondary cation at exchange conditions thereby exchanging the A cation for the secondary cation.

18. The product of the process of claim 10.

19. The product of the process of claim 17.

20. A process for the ammoxidation of alkanes comprising reacting an alkane with ammonia in the presence of oxygen over an ammoxidation catalyst at ammoxidation conditions to produce a nitrile, where the alkane is selected from the group consisting of propane, isobutane and mixtures thereof and the ammoxidation catalyst comprises a crystalline composition having an empirical formula of:

21. The process of claim 20 where the alkane is propane.

22. The process of claim 20 where the alkane is isobutane.

23. The process of claim 20 where the source of oxygen is air.

24. The process of claim 20 where the ammoxidation conditions include a temperature of about 350°

C. to about 700°

C., an hourly space velocity of about 100 to about 10,000 hr<sup>−

1</sup>, an ammonia to alkane mole ratio of about 0.5;

1 to about 3;

1, an oxygen to ammonia mole ratio of about 0.5;

1 to about 10;

1.