Catalyst comprising chromium and zirconium for the polymerization and/or copolymerization of olefins
Catalyst for the polymerization and/or copolymerization of olefins which is obtainable by application to a finely divided inorganic support and concluding calcination at temperatures of from 350 to 1050° C. and has a chromium content of from 0.1 to 5% by weight and a zirconium content of from 0.5 to 10% by weight, in each case based on the element in the finished catalyst, with the molar ratio of zirconium to chromium being from 0.6 to 5.
1. A process for preparing an ethylene polymer comprising polymerizing ethylene or ethylene with C 3 -C 20 -olefins as comonomers in the presence of a polymerization catalyst, the catalyst being obtained by a process comprising:
supporting compounds selected from the group consisting of chromium compound(s) and zirconium compound(s), and optionally a fluorinating agent, with an organic polar solvent onto a finely divided inorganic support having a pore volume, thereby forming a treated support; and
calcining the treated support at a temperature of from 350 to 1050° C. under oxidative conditions,
the catalyst having a chromium content of from 0.1 to 5% by weight, a zirconium content of from 0.5 to 10% by weight, in each case based on the element in the finished catalyst, and a molar ratio of zirconium to chromium from 0.6 to 5.
2. The process according to claim 1 wherein the chromium content of the catalyst is from 0.2 to 3% by weight.
3. The process according to claim 1 wherein the zirconium content of the catalyst is from 0.5 to 5% by weight.
4. The process according to claim 1 wherein the molar ratio of zirconium to chromium in the catalyst is from 0.7 to 3.
5. The process according to claim 1 wherein the catalyst further comprises a fluorine content of from 0.5 to 3% by weight, based on the element in the finished catalyst.
6. The process according to claim 1 wherein the catalyst support is obtained by a process comprising at least one spray drying step.
7. The process according to claim 1 wherein the support is obtained by a process comprising:
i) preparing a hydrogel;
ii) milling the hydrogel to give a finely particulate hydrogel in which at least 5% by volume of the particles, based on the total volume of the particles, have a particle size in the range from >0 μm to ≦3 μm, and/or at least 40% by volume of the particles, based on the total volume of the particles, have a particle size in the range from >0 μm to ≦12 μm, and/or at least 75% by volume of the particles, based on the total volume of the particles, have a particle size in the range from >0 μm to ≦35 μm;
iii) producing a slurry comprising the finely particulate hydrogel; and
iv) dying the slurry.
8. The process according to claim 1 wherein the catalyst is prepared by a process comprising:
(a) preparing an inorganic, finely divided support;
(b) applying the chromium compound to the finely divided support;
(c) applying the zirconium compound to the support;
(d) optionally, removing the solvent from the solid; and
(e) calcining the solid at a temperature of from 350 to 1050° C., under oxidative conditions,
wherein steps (b) and (c) can be carried out together or separately, in any order.
9. The process according to claim 8 wherein the catalyst is prepared by a process comprising:
(a) preparing the inorganic, finely divided support;
(b2) preparing a homogeneous solution comprising an organic or inorganic chromium compound and a zirconium compound in a protic or aprotic polar solvent;
(c2) contacting the solution from (b2) with the finely divided inorganic support;
(d) optionally, removing the solvent from the solid; and
(e) calcining the solid at a temperature of from 350 to 1050° C., under oxidative conditions.
10. The process according to claim 8 wherein no further calcination apart from step (e) is carried out.
11. The process according to claim 8 further comprising an amount of solution in steps (b) or (c) smaller than the pore volume of the support.
12. The process according to claim 8 wherein the solvent is an alcohol, ether, ketone or ester.
13. The process according to claim 8 wherein the chromium compounds are salts of trivalent chromium with an organic or inorganic acid.
14. The process according to claim 8 wherein the zirconium compounds are selected from the group consisting of ZrCl 4 , ZrO(NO 3 ) 2 , and Zr(OR) 4 , where R is a C 1 -C 20 -hydrocarbon radical.
15. The process according to claim 1 wherein the polymerization is carried out at a pressure of from 0.5 to 6 MPa and a temperature of from 30 to 150° C. in a reactor containing a fluidized bed or suspension of finely particulate polymer.
16. The process according to claim 1 wherein the polymer is a powder having a poured density of at least 460 kg/m 3 .
17. The process according to claim 2 wherein the chromium content of the catalyst is from 0.3 to 1.5%.
18. The process according to claim 3 wherein the zirconium content of the catalyst is from 2 to 4%.
19. The process according to claim 4 wherein the molar ratio of zirconium to chromium in the catalyst is from 0.75 to 2.5.
20. The process according to claim 8 wherein the temperature of step (e) is from 400 to 950° C.
21. The process according to claim 9 wherein the temperature of step (e) is from 400 to 950° C.
22. The process according to claim 8 further comprising an amount of solution used in step (c2) smaller than the pore volume of the support.
23. The process of claim 12 wherein the solvent is an alcohol.
24. The process according to claim 13 wherein the salts of trivalent chromium are acetates, oxalates, sulfates or nitrates.
25. The process according to claim 14 wherein the zirconium compounds are zirconium(IV) propoxide, Zr(OOCR) 4 , zirconium acetate, M 4 Zr(C 2 O 4 ) where M is an alkali metal, (NH 4 ) 4 Zr(C 2 O 4 ) 4 , zirconium acetylacetonate or mixtures thereof.
26. The process of claim 16 wherein the poured density is at least 470 kg/m 3 .