Calcination process to produce enhanced odh catalyst

Patent metadata

Field	Value
Publication number	US-2019291080-A1
Application number	US-201916358802-A
Country	US
Kind code	A1
Filing date	Mar 20, 2019
Priority date	Mar 26, 2018
Publication date	Sep 26, 2019
Grant date	—

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 to calcine a catalyst precursor of the formula
Mo 1 V 0.1-1 V 0.1-1 Nb 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 the valence of the catalyst while maintaining an amorphous content of not less than 40 wt. % the method comprising
calcining the catalyst precursor 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 rate of flow comparable to a flow rate of not less 150 sccm through a 2.54 cm diameter tube, with a length of 152 cm at a pressure of greater than or equal to 1 psig 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 said catalyst precursor being fully or partially enclosed by a porous material having a melting temperature greater than 600° C.

2 . The method according to claim 1 , wherein the inert container is made from high temperature glass, quartz, ceramics, or steel.

3 . The method according to claim 2 , wherein the inert container has a heat conductivity greater than 0.34 W m −1 ·K.

4 . The method according to claim 1 , wherein the pressure of inert gas is greater than 1 psig.

5 . The method according to claim 4 , wherein rate for heating the catalyst precursor is 0.9 to 2.0 C per min.

6 . The method according to claim 4 , wherein the catalyst precursor is held at the holding temperature from 2-24 hours.

7 . The method according to claim 6 , wherein the holding temperature is from 400° C. to 525° C.

8 . The method according to claim 7 , wherein the inert gas and comprises nitrogen.

9 . The method according to claim 8 , wherein the porous material is chosen from glass and mineral fiber.

10 . The method according to claim 9 , wherein charcoal or activated carbon is on the outer surface of the porous material in an amount up to 0.5 g per 1 g of catalyst precursor is present on the upper surface of the material.

11 . The method according to claim 10 , wherein X is one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof.

12 . The method according to claim 11 , wherein the molar ratio of said 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.

13 . The method according to claim 12 , wherein the X is chosen from of one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu and mixtures thereof.

14 . The method according to claim 13 , wherein in the catalyst precursor X is absent.

15 . The method according to claim 14 , wherein the catalyst precursor has the formula:
MoV 1.0 V 0.10-049 Te 0.06-0.17 Nb 0.13-0.19 O d .

16 . A calcined catalyst of the formula:
Mo 1 V 0.40-0.45 Te 0.10-0.16 Nb 0.13-0.16 O d .

17 . A calcined catalyst of the formula
MoVo 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. %.

18 . A calcined catalyst according to claim 17 having a crystallite size calculated according to the Scherrer equation of 45 to 55 nm.

19 . A calcined catalyst according to claim 17 having a crystallite size calculated according to the Scherrer equation of 50 to 52 nm.

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

21 . A method for the 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 and optionally one or more C 3-6 alkanes or alkenes and oxygenated species including CO and CO 2 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 said mixture over the catalyst of claim 1 .

22 . A method for the 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 and optionally one or more C 3-6 alkanes or alkenes and oxygenated species including CO and CO 2 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 said mixture over the catalyst of claim 17 .

Assignees

• Nova Chem Int Sa

Inventors

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

Classifications

• B01J2523/64

  Tellurium · CPC title

• B01J2523/56

  Niobium · CPC title

• C07C2527/057

  Selenium or tellurium; Compounds thereof · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J6/001

  Calcining · CPC title