Selective ammoxidation catalysts

Patent metadata

Field	Value
Publication number	US-9358528-B2
Application number	US-201514935514-A
Country	US
Kind code	B2
Filing date	Nov 9, 2015
Priority date	May 29, 2014
Publication date	Jun 7, 2016
Grant date	Jun 7, 2016

Abstract

A catalytic composition useful for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile, and mixtures thereof. The catalytic composition comprises a complex of metal oxides comprising bismuth, molybdenum, iron, cerium and other promoters, wherein the ratio of bismuth to cerium ratio in the composition is greater than or equal to 0.45 and less than or equal to 1.5.

First claim

The claimed invention is:

1. A process for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile, and mixtures thereof, respectively, by reacting in the vapor phase at an elevated temperature and pressure said olefin with a molecular oxygen containing gas and ammonia in the presence of a catalyst wherein the relative ratios of the listed elements in said catalyst are represented by the following formula:
Mo m Bi a Fe b A c D d E e F f G g Ce h O x

wherein
A is at least one element selected from the group consisting of sodium, potassium, rubidium and cesium; and
D is at least one element selected from the group consisting of nickel, cobalt, manganese, zinc, magnesium, calcium, strontium, cadmium and barium;
E is at least one element selected from the group consisting of chromium, tungsten, boron, aluminum, gallium, indium, phosphorus, arsenic, antimony, vanadium and tellurium;
F is at least one element selected from the group consisting of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium thulium, ytterbium, lutetium, scandium, yttrium, titanium, zirconium, hafnium, niobium, tantalum, aluminum, gallium, indium, thallium, silicon, germanium and less than about 10 ppm lead;
G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and

a, b, c, d, e, f, g, h and x are, respectively, the atomic ratios of bismuth (Bi), iron (Fe), A, D, E, F, G, cerium (Ce) and oxygen (O), relative to “m” atoms of molybdenum (Mo), wherein
a is from 0.05 to 7,
b is from 0.1 to 7,
c is from 0.01 to 5,
d is from 0.1 to 12,
e is from 0 to 5,
f is from 0 to 5,
g is from 0 to 0.2,
h is from 0.01 to 5,
m is from 10 to 15, and
x is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present;

wherein 0.5≦a/h≦1.5 and 0.3≦(a+h)/d≦1 and 0.8≦a/h≦5.

2. A process for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrolein/acrylic acid, methacrolein/methacrylic acid, and mixtures thereof, respectively, by reacting in the vapor phase at an elevated temperature and pressure said olefin with a molecular oxygen containing gas in the presence of a catalyst wherein the relative ratios of the listed elements in said catalyst are represented by the following formula:
Mo m Bi a Fe b A c D d E e F f G g Ce h O x

wherein
A is at least one element selected from the group consisting of sodium, potassium, rubidium and cesium; and
D is at least one element selected from the group consisting of nickel, cobalt, manganese, zinc, magnesium, calcium, strontium, cadmium and barium;
E is at least one element selected from the group consisting of chromium, tungsten, boron, aluminum, gallium, indium, phosphorus, arsenic, antimony, vanadium and tellurium;
F is at least one element selected from the group consisting of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium thulium, ytterbium, lutetium, scandium, yttrium, titanium, zirconium, hafnium, niobium, tantalum, aluminum, gallium, indium, thallium, silicon, germanium and less than about 10 ppm lead;
G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and

a, b, c, d, e, f, g, h and x are, respectively, the atomic ratios of bismuth (Bi), iron (Fe), A, D, E, F, G, cerium (Ce) and oxygen (O), relative to “m” atoms of molybdenum (Mo), wherein
a is from 0.05 to 7,
b is from 0.1 to 7,
c is from 0.01 to 5,
d is from 0.1 to 12,
e is from 0 to 5,
f is from 0 to 5,
g is from 0 to 0.2,
h is from 0.01 to 5,
m is from 10 to 15, and
x is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present;

wherein 0.5≦a/h≦1.5 and 0.3≦(a+h)/d≦1 and 0.8≦a/h≦5.

3. The process of claim 1 , wherein 0.65≦a/h<1.5.

4. The process of claim 1 , wherein 0.7≦a/h<1.5.

5. The process of claim 1 , wherein 0.8≦a/h<1.5.

6. The process of claim 1 , wherein 0.90≦a/h<1.5.

7. The process of claim 1 , wherein 0.90≦a/h<1.2.

8. The process of claim 2 , wherein 0.65≦a/h<1.5.

9. The process of claim 2 , wherein 0.7≦a/h<1.5.

10. The process of claim 2 , wherein 0.8≦a/h<1.5.

11. The process of claim 2 , wherein 0.90≦a/h<1.5.

12. The process of claim 2 , wherein 0.90≦a/h≦1.2.

Assignees

• Ineos Europe Ag

Inventors

• Brazdil James F
• Toft Mark A
• Besecker Charles J
• Seely Michael J

Classifications

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J23/887 Primary

  containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• B01J23/8993 Primary

  with chromium, molybdenum or tungsten · CPC title

• C07C11/06

  Propene · CPC title