Process for polymerizing ethylene in a multi-stage polymerization process
The present invention is concerned with a process for polymerizing ethylene or copolymerizing ethylene and at least one alpha-olefin comonomer in the presence of a supported polymerization catalyst in a multi-stage process in which the last polymerization stage is a gas phase reactor, the use of said process for reducing particle carry-over in the last polymerization stage and the use of a supported polymerization catalyst with a certain median particle size to polymerize an ethylene homo- or copolymer in said multi-stage process with a span of its particle size distribution which can be predicted from the median particle size of the catalyst.
1. A process for polymerizing ethylene or copolymerizing ethylene and at least one alpha-olefin comonomer with 3 to 12 carbon atoms in the presence of a supported polymerization catalyst in a multi-stage polymerization process in which at least two polymerization stages are connected in series and a last polymerization stage is conducted in a gas phase reactor to obtain an ethylene homo- or copolymer, wherein
(a) in the first polymerization stage, which is not a pre-polymerization stage, the catalyst activity is at least 15 kg/g catalyst /h; and
(b) in each polymerization stage subsequent to said first polymerization stage, the catalyst activity is not more than 75% of the catalyst activity in said first polymerization stage.
2. The process according to claim 1 , wherein the supported polymerization catalyst is selected from a supported Ziegler-Natta catalyst gr a supported metallocene catalyst.
3. The process according to claim 1 , wherein the supported polymerization catalyst is selected from a silica supported polymerization catalyst, a MgCl 2 -supported polymerization catalyst, a silica/MgCl 2 -supported polymerization catalyst, or a self-supported polymerization catalyst.
4. The process according to claim 1 , wherein the supported polymerization catalyst has a skeletal catalyst density of more than 1.3 g/ml.
5. The process according to claim 1 , wherein the supported polymerization catalyst has a median particle size d 50cat of from 5 to 30 μm.
6. The process according to claim 1 , wherein the particle size distribution of the supported polymerization catalyst (PSD cat ) has a relative span of less than 1.6, wherein the relative span follows the equation (I)
span cat =( d 90cat −d 10cat )/ d 50cat (I)
wherein
span cat is the relative span of the particle size distribution of the supported polymerization catalyst (PSD cat );
d 90cat is the diameter of the particles of the supported polymerization catalyst at which 90% of the sample's mass is comprised of particles with a diameter less than this value in μm,
d 50cat is the diameter of the particles of the supported polymerization catalyst at which 50% of the sample's mass is comprised of particles with a diameter less than this value (median particle size) in μm, and
d 10cat is the diameter of the particles of the supported polymerization catalyst at which 10% of the sample's mass is comprised of particles with a diameter less than this value in μm.
7. The process according to claim 1 , wherein the last polymerization stage is conducted in a fluidized bed reactor comprising a comprising a distribution plate and a disengaging zone and the particle size distribution of the supported catalyst particles (PSD cat ), in the last polymerization stage, has a relative span following the inequation (II)
span cat ≤2.4−0.16· d 50cat +0.0107· d 50cat 2 −2.58·10 −4 ·d 50cat 3 (II)
wherein
span cat is the relative span of the particle size distribution of the supported catalyst particle (PSD cat ) in the last polymerization stage and is defined by the formula span cat =(d 90cat −d 10cat )/d 50cat ; wherein
d 50cat is the diameter of the particles of the supported polymerization catalyst at which 50% of the sample's mass is comprised of particles with a diameter less than this value (median particle size) in μm;
d 90cat is the diameter of the particles of the supported polymerization catalyst at which 90% of the sample's mass is comprised of particles with a diameter less than this value in μm, and
d 10cat is the diameter of the particles of the supported polymerization catalyst at which 10% of the sample's mass is comprised of particles with a diameter less than this value in μm.
8. The process according to claim 1 , wherein the last polymerization stage is conducted in a double cone reactor and the particle size distribution of the supported catalyst particles (PSD cat ), in the last polymerization stage, has a relative span following the inequation (III)
span cat ≤2.81−0.20· d 50cat +0.0131· d 50cat 2 −3.12·10 −4 ·d 50cat 3 (III)
wherein
span cat is the relative span of the particle size distribution of the supported catalyst particles (PSD cat ) in the last polymerization stage and is defined by the formula span cat =(d 90cat −d 10cat )/d 50cat ;
d 50cat is the diameter of the particles of the supported polymerization catalyst at which 50% of the sample's mass is comprised of particles with a diameter less than this value (median particle size) in μm;
d 90cat is the diameter of the particles of the supported polymerization catalyst at which 90% of the sample's mass is comprised of particles with a diameter less than this value in μm, and
d 10cat is the diameter of the particles of the supported polymerization catalyst at which 10% of the sample's mass is comprised of particles with a diameter less than this value in μm.
9. The process according to claim 1 , wherein the particle size d 90 of the ethylene homo- or copolymer, (d 90PE ), which is the diameter of the particles of the supported polymerization catalyst at which 90% of the sample's mass is comprised of particles with a diameter less than this value in μm, in the last polymerization stage, is within the range of from 300 μm to 1500 μm.
10. The process according to claim 1 , wherein the first polymerization stage, which is not a pre-polymerization stage, is conducted in a slurry phase reactor.
11. The process according to claim 1 , which is a continuous mode multi-stage polymerization process.
12. A process of conducting polymerization of an ethylene homo- or copolymer comprising utilizing supported polymerization catalyst particles having a median particle size d 50cat of from 5 to 30 μm in a multi-stage polymerization process in which at least two polymerization stages are connected in series and the last polymerization stage is conducted in a gas phase reactor, wherein
(a) in a first polymerization stage, which is not a pre-polymerization stage, the catalyst activity is at least 15 kg/g catalyst /h;
(b) in each polymerization stage subsequent to said first polymerization stage, the catalyst activity is not more than 75% of the catalyst activity in said first polymerization stage; and
(c) the particle size distribution of the supported polymerization catalyst particles (PSD cat ) has a relative span following the inequation (II)
span cat ≤2.4−0.16· d 50cat +0.0107· d 50cat 2 −2.58·10 −4 ·d 50cat 3 (II),
wherein:
span cat is the relative span of the particle size distribution of the supported polymerization catalyst particles (PSD cat ) and is defined by the formula span cat =(d 90cat −d 10cat )/d 50cat ;
d 50cat is the diameter of the supported polymerization catalyst at which 50% of a sample's mass is comprised of particles with a diameter less than this value (median particle size) in μm;
d 90cat is the diameter of the particles of the supported polymerization catalyst at which 90% of the sample's mass is comprised of particles with a diameter less than this value in μm, and
d 10cat is the diameter of the particles of the supported polymerization catalyst at which 10% of the sample's mass is comprised of particles with a diameter less than this value in μm.
13. A process of conducting polymerization of an ethylene homo- or copolymer comprising utilizing supported polymerization catalyst particles having a median particle size d 50cat of from 5 to 30 μm in a multi-stage polymerization process in which at least two polymerization stages are connected in series and a last polymerization stage is conducted in a double cone reactor wherein
(a) in a first polymerization stage, which is not a pre-polymerization stage, the catalyst activity is at least 15 kg/g catalyst /h;
(b) in each polymerization stage subsequent to said first polymerization stage, the catalyst activity is not more than 75% of the catalyst activity in said first polymerization stage; and
(c) the particle size distribution of the supported polymerization catalyst particles (PSDcat) has a relative span following the inequation (II)
span cat ≤2.81−0.20· d 50cat +0.0131· d 50cat 2 −3.12·10 −4 ·d 50cat 3 (III)
wherein:
span cat is a relative span of the particle size distribution of the supported polymerization catalyst particles (PSD cat ) and is defined by the formula span cat =(d 90cat −d 10cat )/d 50cat ;
d 50cat is the diameter of the particles of the supported polymerization catalyst at which 50% of a sample's mass is comprised of particles with a diameter less than this value (median particle size) in μm;
d 90cat is the diameter of the particles of the supported polymerization catalyst at which 90% of the sample's mass is comprised of particles with a diameter less than this value in μm, and
d 10cat is the diameter of the particles of the supported polymerization catalyst at which 10% of the sample's mass is comprised of particles with a diameter less than this value in μm.