Methods for producing metal-containing sulfated activator-supports
The present invention provides metal-containing sulfated activator-supports, and polymerization catalyst compositions employing these activator-supports. Methods for making these metal-containing sulfated activator-supports and for using such components in catalyst compositions for the polymerization of olefins are also provided.
1. A process to produce a metal-containing sulfated activator-support comprising:
(a) contacting a solid oxide with a sulfate compound to produce a sulfated solid oxide;
(b) calcining the sulfated solid oxide to produce a calcined sulfated solid oxide; and
(c) contacting the calcined sulfated solid oxide with a vapor comprising a transition metal compound;
to produce the metal-containing sulfated activator-support.
2. The process of claim 1 , wherein the sulfate compound comprises sulfuric acid, ammonium sulfate, or a combination thereof.
3. The process of claim 1 , wherein the transition metal compound comprises titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, iron, cobalt, nickel, copper, scandium, yttrium, lanthanum, or any combination thereof.
4. The process of claim 1 , wherein the solid oxide is calcined prior to step (a).
5. The process of claim 1 , wherein the metal-containing sulfated activator-support is not calcined.
6. A process to produce a metal-containing sulfated activator-support comprising:
(a) contacting a solid oxide with a sulfate compound while calcining to produce a calcined sulfated solid oxide; and
(b) contacting the calcined sulfated solid oxide with a vapor comprising a transition metal compound;
to produce the metal-containing sulfated activator-support.
7. The process of claim 6 , wherein the sulfate compound comprises sulfuric acid, ammonium sulfate, or a combination thereof.
8. The process of claim 6 , wherein:
the transition metal compound comprises titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, iron, cobalt, nickel, copper, scandium, yttrium, lanthanum, or any combination thereof; and
the solid oxide comprises silica, alumina, silica-alumina, aluminophosphate, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or any combination thereof.
9. The process of claim 6 , wherein the solid oxide is calcined prior to step (a).
10. The process of claim 6 , wherein the metal-containing sulfated activator-support is not calcined.
11. The process of claim 6 , wherein a weight percent of the transition metal compound to the metal-containing sulfated activator-support is in a range from about 0.01 to about 10 percent.
12. The process of claim 6 , wherein:
the transition metal compound comprises titanium, zirconium, hafnium, vanadium, or any combination thereof; and
the solid oxide comprises silica, alumina, silica-alumina, or any combination thereof.
13. The process of claim 1 , wherein the solid oxide comprises silica, alumina, silica-alumina, aluminophosphate, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or any combination thereof.
14. The process of claim 1 , wherein in step (b), the sulfated solid oxide is calcined at a temperature in a range from about 350° C. to about 600° C. for about 0.3 to about 20 hours.
15. The process of claim 1 , wherein a weight percent of the transition metal compound to the metal-containing sulfated activator-support is in a range from about 0.01 to about 10 percent.
16. The process of claim 1 , wherein:
the transition metal compound comprises titanium, zirconium, hafnium, vanadium, or any combination thereof; and
the solid oxide comprises silica, alumina, silica-alumina, or any combination thereof.
17. The process of claim 16 , wherein:
the transition metal compound comprises TiCl 4 ; and
the ratio of the sulfate compound to the solid oxide is greater than about 0.5 mmol/g.
18. The process of claim 12 , wherein:
the transition metal compound comprises TiCl 4 ; and
the ratio of the sulfate compound to the solid oxide is greater than about 0.5 mmol/g.
19. The process of claim 16 , wherein a weight percent of the transition metal compound to the metal-containing sulfated activator-support is in a range from about 0.1 to about 5 percent.
20. The process of claim 12 , wherein a weight percent of the transition metal compound to the metal-containing sulfated activator-support is in a range from about 0.1 to about 5 percent.