# US 11,998,895 B2 · Oxidative dehydrogenation catalyst compositions

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- Number: US 11,998,895 B2
- Document ID: US11998895B2
- Status: Granted
- Kind: B2
- Application number: 17/860,143
- Filed: 2022-07-08
- Published: 2023-09-07
- Granted: 2024-06-04
- Earliest claimed: 2018-08-03
- Assignees: NOVA Chemicals (International) S.A.
- Applicants: NOVA Chemicals (International) S.A.
- Inventors: Vasily Simanzhenkov; Xiaoliang Gao; Marie Barnes; David Sullivan; Yoonhee Kim
- Web page: https://patentgrep.com/patent/US11998895B2

## CPC

- B01J 23/28: Molybdenum
- B01J 21/04: Alumina
- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 27/0576: {Tellurium; Compounds thereof}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C07C 5/48: with oxygen as an acceptor
- C10G 11/02: characterised by the catalyst used
- B01J 35/80: characterised by their amorphous structures
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- B01J 2523/55: Vanadium
- B01J 2523/56: Niobium
- B01J 2523/64: Tellurium
- B01J 2523/68: Molybdenum
- C07C 2521/04: Alumina
- C07C 2523/20: Vanadium, niobium or tantalum
- C07C 2523/22: Vanadium
- C07C 2523/28: Molybdenum
- C07C 2523/32: Manganese, technetium or rhenium
- C07C 2527/057: Selenium or tellurium; Compounds thereof
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided in this disclosure are catalyst compositions. The catalyst compositions include an oxidative dehydrogenation catalyst that includes a mixed metal oxide having the empirical formula: Mo1.0V0.12-0.49Te0.05-0.17Nb0.10-0.20AlcOd wherein c is from 0 to 2.0 and d is a number to satisfy the valence of the oxide. The compositions are at least 40 wt. % amorphous as measured by XRD. The disclosure also provides methods of making the compositions.

## Claims

### Claim 1

A method of preparing a catalyst composition comprising
providing a mixture comprising alumina, water, and an oxidative dehydrogenation catalyst precursor comprising a mixed metal oxide having the empirical formula:
Mo1.0V0.12-0.49Te0.05-0.25Nb0.10-0.20Od
heating the mixture comprising the oxidative dehydrogenation catalyst precursor, the alumina, and the water to remove at least 40 wt. % of the water to provide a pre-calcination catalyst composition, and
calcining the pre-calcination catalyst composition to provide the catalyst composition having the empirical formula:
Mo1.0V0.12-0.49Te0.05-0.25Nb0.10-0.20Al0.01-2.0Od
wherein d is a number to satisfy the valence of the oxide, wherein the catalyst composition is from 60 wt. % to 80 wt. % amorphous.

### Claim 2 (depends on 1)

The method of claim 1, wherein the mixture comprises:
about 20 wt. % to about 90 wt. % of the water,
about 5 wt. % to about 50 wt. % of the oxidative dehydrogenation catalyst precursor, and
about 5 wt. % to about 30 wt. % of the alumina.

### Claim 3 (depends on 1)

The method of claim 1, wherein the mixture is heated at a temperature of about 60° C. to about 100° C.

### Claim 4 (depends on 1)

The method of claim 1, wherein heating the mixture removes about 50 wt. % to about 99.9 wt. % of the water.

### Claim 5 (depends on 1)

The method of claim 1, wherein the calcination temperature is about 300° ° C. to about 450° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein the catalyst composition has an amorphous content of 5 wt. % to 50 wt. % greater than the predicted additive amorphous content for the catalyst composition.

### Claim 7 (depends on 1)

A method of claim 1, wherein the catalyst composition has the empirical formula:
Mo1.0V0.12-0.49Te0.05-0.25Nb0.10-0.20Al0.5-2.0Od
wherein d is a number to satisfy the valence of the oxide.

### Claim 8 (depends on 1)

A method of claim 1, wherein the catalyst composition has a molar ratio of molybdenum to vanadium from 1:0.12 to 1:0.49, as determined by particle-induced X-ray emission (PIXE).

### Claim 9 (depends on 1)

A method of claim 1, wherein the catalyst composition has a molar ratio of molybdenum to tellurium is from 1:0.05 to 1:0.25, as determined by PIXE.

### Claim 10 (depends on 1)

A method of claim 1, wherein the catalyst composition has a molar ratio of molybdenum to niobium is 15 from 1:0.10 to 1:0.20, as determined by PIXE.

### Claim 11 (depends on 1)

A method of claim 1, wherein the catalyst composition has a molar ratio of molybdenum to aluminum is from 0.01 to 2.0, as determined by PIXE.

### Claim 12

A method of increasing the amorphous phase of a catalyst composition comprising an oxidative dehydrogenation catalyst comprising
providing a mixture comprising the oxidative dehydrogenation catalyst, alumina, and water,
heating the mixture comprising the oxidative dehydrogenation catalyst, the alumina, and the water to remove at least 40 wt. % of the water to provide a pre-calcination catalyst composition, and
calcining the pre-calcination catalyst composition to provide the catalyst composition having the empirical formula:
Mo1.0V0.12-0.49Te0.05-0.25Nb0.10-0.20Al0.1-2.0Od
wherein d is a number to satisfy the valence of the oxide wherein the catalyst composition is from 60 wt. % to 80 wt. % amorphous.

### Claim 13 (depends on 12)

A method of claim 12, wherein the catalyst composition has a molar ratio of molybdenum to vanadium from 1:0.12 to 1:0.49, as determined by PIXE.

### Claim 14 (depends on 12)

A method of claim 12, wherein the catalyst composition has a molar ratio of molybdenum to tellurium is from 1:0.05 to 1:0.25, as determined by PIXE.

### Claim 15 (depends on 12)

A method of claim 12, wherein the catalyst composition has a molar ratio of molybdenum to niobium is 15 from 1:0.10 to 1:0.20, as determined by PIXE.

### Claim 16 (depends on 12)

A method of claim 12, wherein the catalyst composition has a molar ratio of molybdenum to aluminum is from 0.01 to 2.0, as determined by PIXE.

### Claim 17 (depends on 12)

A method of claim 12, wherein the catalyst composition has the empirical formula:
Mo1.0V0.12-0.49Te0.05-0.25Nb0.10-0.20Al0.5-2.0Od
wherein d is a number to satisfy the valence of the oxide.