Calcination process to produce enhanced ODH catalyst

Patent metadata

Field	Value
Publication number	US-12208373-B2
Application number	US-202318303236-A
Country	US
Kind code	B2
Filing date	Apr 19, 2023
Priority date	Mar 26, 2018
Publication date	Jan 28, 2025
Grant date	Jan 28, 2025

Abstract

Mixed metal oxide catalysts having an amorphous content of not less than 40 wt. % are prepared by calcining the catalyst precursor fully or partially enclosed by a porous material having a melting temperature greater than 600° C. in an inert container including heating the catalyst precursor at a rate from 0.5 to 10° C. per minute from room temperature to a temperature from 370° C. to 540° C. under a stream of pre heated gas chosen from steam and inert gas and mixtures thereof at a pressure of greater than or equal to 1 psig having a temperature from 300° C. to 540° C. and holding the catalyst precursor at that temperature for at least 2 hours and cooling the catalyst precursor to room temperature.

First claim

What is claimed is:

1. A method for oxidative dehydrogenation of a mixed feed comprising one or more C 2-4 paraffins and oxygen in a volume ratio from 70:30 to 95:5 at a temperature from 320° C. up to 385° C., a gas hourly space velocity of not less than 100 hr −1 , and a pressure from 0.8 to 7 atmospheres comprising passing the mixed feed over a catalyst of formula
Mo 1 V 0.1-1 Nb 0.1-1 Te 0.01-0.2 X 0-2 O d
where X is chosen from Pd, Sb, Ba, Al, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, Ca, oxides thereof and mixtures thereof, and d is a number to satisfy valence of the catalyst, wherein the mixed feed comprises at least one of carbon monoxide (CO) or carbon dioxide (CO 2 ).

2. The method of claim 1 , wherein the mixed feed comprises at least one of C 3-6 alkanes or alkenes.

3. The method of claim 1 , wherein X is one or more metals and oxides thereof chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof.

4. The method of claim 3 , wherein a molar ratio of the one or more metals and oxides chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof to Mo is from 1:0.001-0.3.

5. The method of claim 4 , wherein X is the one or more metals and oxides thereof chosen from Pd, Sb, Ba, Al, Cu and mixtures thereof.

6. The method of claim 1 , wherein in the catalyst, X is absent.

7. The method of claim 6 , wherein the catalyst has the formula:
Mo 1.0 V 0.10-0.49 Te 0.06-0.17 Nb 0.13-0.19 O d .

8. The method of claim 1 , wherein the catalyst comprises a calcined catalyst prepared by:
calcining a catalyst precursor of same formula in an inert container with flow passage there through, at a rate from 0.5 to 10° C. per minute from room temperature to a holding temperature from 370° C. to 540° C. under a stream of pre heated gas chosen from steam and inert gas and mixtures thereof at a flow rate of not less than 150 sccm at a pressure of greater than or equal to 1 psig, the stream of pre heated gas having a temperature from 300° C. to 540° C.;
holding the catalyst precursor at the holding temperature for at least 2 hours; and
cooling the catalyst precursor to room temperature, the catalyst precursor being fully or partially enclosed by a porous material having a melting temperature greater than 600° C.

9. The method of claim 8 , wherein the inert container is made from glass, quartz, ceramics, or steel, wherein the inert container has a heat conductivity greater than 0.34 W·m −1 ·K, and wherein the porous material is chosen from glass and mineral fiber.

10. The method of claim 8 , wherein the rate for heating the catalyst precursor is 0.9 to 2.0° C. per min.

11. The method of claim 8 , wherein the catalyst precursor is held at the holding temperature from 2-24 hours.

12. The method of claim 11 , wherein the holding temperature is from 400° C. to 525° C.

13. The method of claim 8 , wherein charcoal or activated carbon is present on an outer surface of the porous material in an amount up to 0.5 g per 1 g of catalyst precursor.

14. A method for oxidative dehydrogenation of a mixed feed comprising one or more C 2-4 paraffins and oxygen in a volume ratio of the one or more C 2-4 paraffins to oxygen from 70:30 to 95:5 at a temperature from 320° C. up to 385° C., a gas hourly space velocity of not less than 100 hr −1 , and a pressure from 0.8 to 7 atmospheres comprising passing the mixed feed over a calcined catalyst of formula
MoV 0.40-0.45 Te 0.10-0.16 Nb 0.13-0.16 O d
having an amorphous content of not less than 40 wt. %, and having a crystallite size calculated according to Scherrer equation of 45 to 55 nm.

15. The method of claim 14 , wherein the mixed feed comprises at least one of carbon monoxide (CO) or carbon dioxide (CO 2 ).

16. The method of claim 14 , wherein the mixed feed comprises one or more C 3-6 alkanes or alkenes.

17. The method of claim 14 , wherein the calcined catalyst having a crystallite size calculated according to the Scherrer equation of 50 to 52 nm.

18. The method of claim 14 wherein the calcined catalyst is bound, agglomerated, filled, promoted, impregnated, or supported with from 5 to 90 wt. % of a material other than active phase.

Assignees

• Nova Chemicals International Sa

Inventors

• Simanzhenkov Vasily
• Gao Xiaoliang
• Sullivan David
• Styles Yipei
• Kim Yoonhee
• Drag Hanna
• Barnes Marie

Classifications

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/80

  characterised by their amorphous structures · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title