Selective ammoxidation catalysts

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, with a desirable composition.

The claimed invention is: 
     
         1 . A catalytic composition comprising a complex of metal oxides 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 Ni i Co j Mn k Mg l O #     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 zinc, 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 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, 
 i is from 0.1 to 12, 
 j is from 0.1 to 12, 
 k is from 0.1 to 12, 
 l is from 0.1 to 12, 
 m is from 10 to 15, 
 # is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present; wherein z=d+i+j+k+l; and wherein 0.45≦a/h<1.5 and 0.3≦(a+h)/z; 
   wherein   0.2<i/(i+j+k+l).   
     
     
         2 . The catalytic composition of  claim 1 , wherein 0.25≦i/(i+j+k+l). 
     
     
         3 . The catalytic composition of  claim 1 , wherein 0.3≦i/(i+j+k+l). 
     
     
         4 . The catalytic composition of  claim 1 , wherein 0.5≦i/(i+j+k+l). 
     
     
         5 . The catalytic composition of  claim 1 , wherein 0.7≦i/(i+j+k+l). 
     
     
         6 . The catalytic composition of  claim 1 , wherein z=d+i+j+k+l and 0.3≦(a+h)/z≦1. 
     
     
         7 . The catalytic composition of  claim 1 , wherein 0.45≦a/h<1.5. 
     
     
         8 . The catalytic composition of  claim 1 , wherein 0.65≦a/h<1.5. 
     
     
         9 . The catalytic composition of  claim 1 , wherein 0.7≦a/h<1.5. 
     
     
         10 . The catalytic composition of  claim 1 , wherein 0.8≦a/h<1.5. 
     
     
         11 . The catalytic composition of  claim 1 , wherein 0.90≦a/h<1.2. 
     
     
         12 . The catalytic composition of  claim 1 , wherein 0.8≦h/b<5. 
     
     
         13 . The catalytic composition of  claim 1 , wherein 1.2≦h/b<5. 
     
     
         14 . A catalytic composition comprising a complex of metal oxides 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 Ni i Co j Mn k Mg l O #     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 zinc, 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, and lead germanium; 
 G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and 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, 
 i is from 0.1 to 12, 
 j is from 0.1 to 12, 
 k is from 0.1 to 12, 
 l is from 0.1 to 12, 
 m is from 10 to 15, 
 # is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present; 
   wherein 0.45≦a/h<1.5 and 0.3≦(a+h)/z<0.4; wherein z=d+i+j+k+l;   wherein 0.2<i/(i+j+k+l).   
     
     
         15 . A catalytic composition comprising a complex of metal oxides 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 Ni i Co j Mn k Mg l O #     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 zinc, 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, lead and germanium; 
 G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and 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, 
 i is from 0.1 to 12, 
 j is from 0.1 to 12, 
 k is from 0.1 to 12, 
 l is from 0.1 to 12, 
 m is from 10 to 15, 
 # is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present; 
   wherein 0.7≦a/h<1.5 and 0.3≦(a+h)/z; wherein z=d+i+j+k+l;   wherein 0.2<i/(i+j+k+l).   
     
     
         16 . A catalytic composition comprising a complex of metal oxides 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 Ni i Co j Mn k Mg l O #     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 zinc, 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 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, 
 i is from 0.1 to 12, 
 j is from 0.1 to 12, 
 k is from 0.1 to 12, 
 l is from 0.1 to 12, 
 m is from 10 to 15, 
 # is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present; and 
   wherein the cell volume of the M 2+ MoO 4  is defined as β; wherein 625 {acute over (Å)} 3 ≦β≦630 {acute over (Å)} 3 .   
     
     
         17 . The catalytic composition of claim  51 , wherein z=d+i+j+k+l and 0.3≦(a+h)/z<1. 
     
     
         18 . The catalytic composition of claim  51 , wherein 0.45≦a/h<1.5. 
     
     
         19 . A catalytic composition comprising a complex of metal oxides 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 Ni i Co j Mn k Mg l O #     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 zinc, 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, lead and germanium; 
 G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and 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, 
 i is from 0.1 to 12, 
 j is from 0.1 to 12, 
 k is from 0.1 to 12, 
 l is from 0.1 to 12, 
 m is from 10 to 15, 
 # is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present; 
   wherein 0.45≦a/h<1.5 and 0.3≦(a+h)/z≦0.4; wherein z=d+i+j+k+l; and   wherein the cell volume of the M 2+ MoO 4  is defined as β; wherein 625 {acute over (Å)} 3 ≦β≦630 {acute over (Å)} 3 .   
     
     
         20 . A catalytic composition comprising a complex of metal oxides 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 Ni i Co j Mn k Mg l O #     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 zinc, 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, lead and germanium; 
 G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and 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, 
 i is from 0.1 to 12, 
 j is from 0.1 to 12, 
 k is from 0.1 to 12, 
 l is from 0.1 to 12, 
 m is from 10 to 15, 
 # is the number of oxygen atoms required to satisfy the valence requirements of the other component elements present; 
   wherein 0.7≦a/h<1.5 and 0.3≦(a+h)/z; wherein z=d+i+j+k+l; and   wherein the cell volume of the M 2+ MoO 4  is defined as β; wherein 625 {acute over (Å)} 3 ≦β≦630 {acute over (Å)} 3 .