Rapid activation process and activation treatments for chromium catalysts for producing high melt index polyethylenes
Processes for activating chromium polymerization catalysts, which can use lower maximum activation temperatures and shorter activation times than conventional activation methods, and provide polyethylenes with high melt indices, broader molecular weight distributions, and lower long chain branching content. The activation process can comprise heating a supported chromium catalyst in an inert atmosphere to a first temperature (T 1 ) for a first hold time (t H1 ), followed by allowing the chromium catalyst to attain a second temperature (T 2 ) in the inert atmosphere, then contacting the chromium catalyst with an oxidative atmosphere for a second hold time (t H2 ), in which T 2 can be less than or equal to T 1 . Additional activation treatments and conditioning steps are disclosed which can be used to enhance the melt index potential of Phillips (Cr/silica) catalysts.
1. A process for preparing a supported chromium catalyst, the process comprising:
(a) calcining a silicon oxide at a first temperature to provide a calcined silicon oxide comprising siloxane moieties, wherein the first temperature is above 600° C.;
(b) contacting the calcined silicon oxide with a chromium composition comprising a chromium source in an anhydrous, aprotic solvent, to form a chromium-treated silicon oxide comprising a residual solvent, the chromium source comprising a compound of chromium (VI); and
(c) heating the chromium-treated silicon oxide to a second temperature to remove the residual solvent and form the supported chromium catalyst, wherein the second temperature is less than the first temperature.
2. The process of claim 1 , wherein the chromium source comprises CrO 3 , bis(t-butyl)chromate, bis(triphenylsilyl)chromate, diarenechromium(0), chromium tris(acetylacetonate), or CrCl 3 .
3. The process of claim 2 , wherein the chromium composition comprises CrO 3 dissolved in acetonitrile.
4. The process of claim 1 , wherein the supported chromium catalyst comprises, by weight, less than 0.6% Cr(VI).
5. The process of claim 1 , wherein the silicon oxide comprises silica, silica-alumina, silica-titania, titania-coated silica, or a combination thereof.
6. The process of claim 1 , wherein the anhydrous, aprotic solvent comprises acetonitrile, pentane, heptane, dry ether, toluene, a crown ether, or tetrahydrofuran.
7. The process of claim 1 , wherein the first temperature is greater than 800° C.
8. The process of claim 1 , wherein the calcining step is carried out for up to 3 hours.
9. The process of claim 1 , wherein the calcined silicon oxide is substantially dehydroxylated as compared to the silicon oxide prior to being calcined.
10. The process of claim 1 , wherein the second temperature is greater than or equal to 150° C.
11. The process of claim 1 , wherein the chromium-treated silicon oxide is heated to the second temperature for a duration of up to 1 hour.
12. The process of claim 11 , wherein heating the chromium-treated silicon oxide to the second temperature further fixes the chromium to the silicon oxide.
13. The process of claim 1 , wherein during at least a portion of the calcining step, calcining the silicon oxide is carried out in the presence of a dehydroxylation promoter to substantially dehydroxylate the silicon oxide and form the siloxane moieties.
14. The process of claim 1 , wherein at least a portion of the siloxanes are strained siloxanes.
15. A supported chromium catalyst prepared according the process of claim 1 .
16. The supported chromium catalyst of claim 15 , having a catalyst activity of greater than 2 kg g −1 h −1 , greater than 4 kg g −1 h −1 , greater than 6 kg g −1 h −1 , or greater than 8 kg g −1 h −1 .
17. A process for polymerizing olefins using a supported chromium catalyst, the process comprising:
preparing the supported chromium catalyst according to the process of claim 1 ; and
under polymerization conditions, contacting in a reaction zone the supported chromium catalyst with at least one C 2 to C 8 mono-1-olefin to form an olefin polymer.
18. The process of claim 17 , wherein the at least one C 2 to C 8 mono-1-olefin comprises ethylene and at least one C 3 to C 8 mono-1-olefin comonomer.
19. The process of claim 17 , wherein:
the olefin polymer has a melt index (MI) greater than about 10, greater than about 30, or greater than about 50, or greater than about 70.
20. The process of claim 17 , wherein the olefin polymer has a lower long chain branching (LCB) content as compared to a reference polyolefin prepared by an analogous process using a supported chromium catalyst prepared under non-anhydrous conditions.
21. The process of claim 17 , wherein the olefin polymer has a broader molecular weight distribution (MWD) as compared to a reference polyolefin prepared by an analogous process using a supported chromium catalyst prepared under non-anhydrous conditions.