Catalyst on silica clad alumina support
View Patent ↗The invention concerns catalysts comprising (i) a cladded catalyst support comprising (a) a core which comprises alumina particles and (b) about 1 to about 40 weight percent silica cladding, based on the weight of the cladded catalyst support, on the surface of the core; the catalyst support having a BET surface area of greater than 20 m2/g and a porosity of at least about 0.2 cc/g; and (ii) 0.1 to 10 weight percent, based on the weight of the catalyst, of catalytically active transition metal on the surface of the cladded catalyst support; wherein the catalyst support has a normalized sulfur uptake (NSU) of up to 25 ?g/m2. The invention also concerns the production and use of such catalysts.
1. An olefin polymerization catalyst comprising:
(I) a clad catalyst support comprising (a) a core which comprises alumina particles and (b) about 1 to about 40 weight percent silica, based on the weight of said clad catalyst support, clad over the surface of said core; said clad catalyst support having a BET surface area of greater than 20 m 2 /g; a pore volume of at least about 0.2 cc/g; and a Normalized Sulfur Intake (NSU) value of up to 25 μg/m 2 ; and
(II) 0.1 to 10 weight percent, based on the weight of said catalyst, of catalytically active polymerization catalyst selected from elemental transition metal, transition metal compounds, or transition metal complexes, wherein said transition metal is selected form Fe, Cr, Ti, Zr, Hf, Ni, Mg, Pd, or mixtures thereof, immobilized to the surface of said clad catalyst support.
2. The catalyst of claim 1 , wherein said alumina particles comprise particles having an average particle size of from 1 to 500 μm or agglomerates of particles having an average particle size of from 1 to 10 mm or mixtures thereof.
3. The catalyst of claim 1 , wherein said catalyst support has a BET surface area of from 20 to 400 m 2 /g, a pore diameter of from 50 to 1000 Angstroms and a Normalized Sulfur Uptake of up to 15 μg/m 2 .
4. The catalyst of claim 3 wherein said catalyst support has a BET surface area of from 100 to 300 m 2 /g, a pore diameter of from 100 to 300 Angstroms, a pore volume of from 0.5 to 1.2 cc/g, and a Normalized Sulfur Uptake of up to 10 μg/m 2 .
5. The catalyst of claim 1 in which said alumina particulate core is doped with metals or metal oxides chosen from alkaline earth metal oxides, rare earth oxides and silica in an amount of between 0.1 to 10% of the weight of the clad catalyst support.
6. The catalyst of claim 1 , wherein said core has at least 5 weight percent silica clad thereon.
7. The catalyst of claim 1 , wherein said transition metal is selected from Cr, Ti, or mixtures thereof and is present in a high oxidation state.
8. The catalyst of claim 1 , wherein said catalyst is selected from:
(i) at least one transition metal halide, alkyl, aryl, or alkoxy compound and mixtures thereof in combination with Group I through III elements of the Periodic Table;
(ii) organometallic compounds having a transition metal, including rare earth metals, in coordination with members of at least one five-member carbon ring, hetero-substituted five-member carbon ring, or a bridged (ansa) ligand coordinating to a transition or rare earth metal wherein the ansa bridge can be carbon, silicon, phosphorus, sulfur, oxygen, nitrogen, germanium, ethylene, dimethylsilyl, diphenylsilyl, isopropylidene, diphenylphosphoryl, tetramethyldisilane group; or
(iii) a bidentate or tridentate ligand/transition metal complex.
9. The catalyst of any one of claims 1 to 8 , wherein said catalyst component (II) is selected from at least one transition metal halide, alkyl, aryl, or alkoxy compound and mixtures thereof in combination with Group I through III elements of the Periodic Table.
10. The catalyst of claim 1 , wherein said catalyst component (II) is selected from organometallic compounds having a transition metal, including rare earth metals, in coordination with members of at least one five-member carbon ring, hetero-substituted five-member carbon ring, or a bridged (ansa) ligand coordinating to a transition or rare earth metal wherein the ansa bridge can be carbon, silicon, phosphorus, sulfur, oxygen, nitrogen, germanium, ethylene, dimethylsilyl, diphenylsilyl, isopropylidene, diphenylphosphoryl, tetramethyldisilane group.
11. The catalyst of claim 1 , wherein said catalyst component (II) is selected from a bidentate or tridentate ligand/nickel metal complex.
12. The catalyst of claim 1 , where said transition metal is present in an amount of 0.1 to 3 weight percent.
13. The catalyst of claim 9 , wherein said transition metal comprises 0.5-1.5 weight percent Cr and 1-3 weight percent Ti.
14. A process for the preparation of a polymer comprising contacting an olefin with a catalyst of claim 1 .
15. The process of claim 14 , wherein said olefin comprises ethylene.
16. The process of claim 14 , wherein said catalytically active olefin polymerization catalyst comprises chromium.
17. The process of claim 14 , wherein said contacting occurs in the presence of a co-catalyst containing aluminum, boron, or mixtures of these.
18. The process of claim 17 , wherein said co-catalyst is present in a molar ratio of co-catalyst to Cr of 0.1-15 for an aluminum containing co-catalyst or 1-6 for a boron containing catalyst.