Catalyst for the polymerisation of olefins, process for its production and use
Silica supported catalyst composition useful in olefin polymerization, having a SiO 2 content not more than 70 weight %, a transition metal (M) content between 2.5 and 9.1 weight %, a magnesium content between 0.5 and 3.3 weight %, an aluminium content between 0.3 and 5 weight % and a chlorine content between 5 and 30 weight %. The silica support has, prior to addition of catalytically active ingredients, a residual surface hydroxyl content between 0.6 and 2 mmole/g of silica, and the molar ratio of transition metal (M) to magnesium is between 0.3 and 2.5.
1. Silica supported catalyst composition which is useful in olefin polymerization, said composition comprising:
a SiO 2 content not more than 70 weight %;
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %;
and wherein
the said silica support has, prior to addition of catalytically active ingredients, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica, and
the molar ratio of transition metal (M) to magnesium is comprised between 0.3 and 2.5.
2. Catalyst composition which is useful in olefin polymerization comprising:
a SiO 2 content not more than 70 weight %,
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %;
wherein said composition is obtained by a preparation process comprising
in a first stage, the formation of a Mg-M liquid complex (M is a transition metal) in the absence of halogen containing compound by reacting at least one organic oxygen-comprising compound of magnesium with at least one organic oxygen-comprising compound of a transition metal,
in a second stage, the impregnation of a silica support by means of the said Mg-M liquid complex, and
in a subsequent stage, the precipitation of the said Mg-M liquid complex on the silica by means of an halogenated organoaluminium compound,
wherein
during the first stage reaction, the molar amount of the transition metal M added per mole of magnesium is comprised between 0.06 and 4, and
the said silica support has, prior to the Mg-M liquid complex impregnation, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica.
3. Catalyst composition according to claim 2 wherein the silicon dioxide content of the catalyst composition is more than 40 weight %.
4. Process for polymerizing olefins comprising contacting olefins with the catalyst composition according to claim 2 together with a co-catalyst in a continuous slurry phase or a continuous gas phase process for the polymerisation of olefins wherein the co-catalyst is chosen from organometallic compounds of a metal from Groups 1, 2, 12, 13, and 14.
5. Catalyst composition which is useful in olefin polymerization characterised by
a SiO 2 content not more than 70 weight %,
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %;
wherein said composition is obtained by a preparation process comprising
in a first stage, the formation of a Mg-M liquid complex (M is a transition metal) by reacting at least one organic oxygen-comprising compound of magnesium with at least one organic oxygen-comprising compound of a transition metal, wherein the organic oxygen-comprising compounds of magnesium only comprise magnesium-oxygen-organic radical bonds per magnesium atom, to the exclusion of any other bond and wherein the organic oxygen-comprising compounds of a transition metal only comprise transition metal-oxygen-organic radical bonds per transition metal atom, to the exclusion of any other bond,
in a second stage, the impregnation of a silica support by means of the said Mg-M liquid complex, and
in a subsequent stage, the precipitation of the said Mg-M liquid complex on the silica by means of an halogenated organoaluminium compound,
wherein
during the first stage reaction, the molar amount of the transition metal M added per mole of magnesium is comprised between 0.06 and 4, and
the said silica support has, prior to the Mg-M liquid complex impregnation, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica.
6. Catalyst composition according to claim 5 wherein the silicon dioxide content of the catalyst composition is more than 40 weight %.
7. Process for polymerizing olefins comprising contacting olefins with the catalyst composition according to claim 5 together with a co-catalyst in a continuous slurry phase or a continuous gas phase process for the polymerisation of olefins wherein the co-catalyst is chosen from organometallic compounds of a metal from Groups 1, 2, 12, 13, and 14.
8. Gas phase process for the (co-)polymerisation of olefins, comprising contacting olefins with a silica supported polymerisation catalyst having the following characteristics:
a SiO 2 content not more than 70 weight,
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %
wherein
the said silica support has, prior to addition of catalytically active ingredients, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica, and
the molar ratio of transition metal (M) to magnesium is comprised between 0.3 and 2.5, and
wherein the productivity is greater than 10000 g of polymer per g of catalyst, space time yield is greater than 100 kg/m 3 /h and the partial pressure of hydrocarbon condensable under reaction conditions is greater than 2 bar.
9. Catalyst composition according to claim 3 wherein the silicon dioxide content of the catalyst composition is more than 50 weight %.
10. Catalyst composition according to claim 6 wherein the silicon dioxide content of the catalyst composition is more than 50 weight %.
11. The process according to claim 4 wherein the co-catalyst is chosen from one or more trialkylaluminiums.
12. The process according to claim 7 wherein the co-catalyst is chosen from one or more trialkylaluminiums.
13. The catalyst composition according to claim 2 wherein the complex impregnation (second stage) is performed on a silica which has been subjected to a thermal treatment step at a temperature of at least 200° C. for up to 24 hours.
14. The catalyst composition according to claim 13 wherein the thermal treatment step is at a temperature 250° C. to 350° C. for 4 to 10 hours.
15. The catalyst composition according to claim 2 wherein the organic oxygen-comprising compound of magnesium is a magnesium dialkoxide.
16. The catalyst composition according to claim 2 wherein the organic oxygen-comprising compound of a transition metal is a titanium tetraalkoxide, a zirconium tetraalkoxide, or a mixture thereof.
17. The catalyst composition according to claim 2 wherein during the impregnation stage, the amount of liquid complex impregnated in the inorganic support is selected such that the impregnated silica support comprises
a magnesium content comprised between 1 mmole and 2 mmole of magnesium per g of silica support, and
a titanium content comprised between 2 mmole and 4 mmole of titanium per g of silica support.
18. The catalyst composition according to claim 2 wherein the halogenated organoaluminium compound used in the precipitation stage is chosen from organoaluminium compounds corresponding to the general formula A1 RnX3-n, in which R is a hydrocarbon-comprising radical comprising up to 20 carbon atoms, X is a halogen and n is less than or equal to 2.
19. The catalyst composition according to claim 5 wherein the complex impregnation (second stage) is performed on a silica which has been subjected to a thermal treatment step at a temperature of at least 200° C. for up to 24 hours.
20. The catalyst composition according to claim 19 wherein the thermal treatment step is at a temperature 250° C. to 350° C. for 4 to 10 hours.
21. The catalyst composition according to claim 5 wherein the organic oxygen-comprising compound of magnesium is a magnesium dialkoxide.
22. The catalyst composition according to claim 5 wherein the organic oxygen-comprising compound of a transition metal is a titanium tetraalkoxide, a zirconium tetraalkoxide, or a mixture thereof.
23. The catalyst composition according to claim 5 wherein during the impregnation stage, the amount of liquid complex impregnated in the inorganic support is selected such that the impregnated silica support comprises
a magnesium content comprised between 1 mmole and 2 mmole of magnesium per g of silica support, and
a titanium content comprised between 2 mmole and 4 mmole of titanium per g of silica support.
24. The catalyst composition according to claim 5 wherein the halogenated organoaluminium compound used in the precipitation stage is chosen from organoaluminium compounds corresponding to the general formula A1 RnX3-n, in which R is a hydrocarbon-comprising radical comprising up to 20 carbon atoms, X is a halogen and n is less than or equal to 2.