Process for gas-phase polymerization having high bed bulk density
The present invention relates to an improvement for gas-phase olefin polymerization process having relatively high bed bulk density. The improvement involves the use of mixed external electron donors when polymerizing propylene in a gas-phase reactor having a polymer bed with a bulk density greater than 128 kg/m 3 , optionally with one or more comonomers, wherein the mixed electron donor system comprises at least a first external electron donor and a second external electron donor, and wherein the first external electron donor is a carboxylate compound.
1. A polymerization process for making polypropylene or propylene copolymer containing C 2 to C 8 comonomers in a gas phase reactor, the process comprising:
polymerizing propylene, optionally with one or more comonomers, in a single flow-pattern gas-phase reactor having a polymer bed with a bed bulk density greater than 128 kg/m 3 , in the presence of a catalyst composition comprising a procatalyst composition and a cocatalyst composition, and a mixed electron donor system, wherein:
a) the mixed electron donor system includes at least a first external electron donor and at least a second external electron donor, the mixed electron donor system comprising at least one selectivity control agent and at least one activity limiting agent, and wherein one of the external electron donors is a carboxylate compound; and
b) the gas-phase reactor having a superficial gas velocity that is less than 10 times the minimum fluidization velocity; and wherein the gas-phase reactor has a solid holdup larger than 0.17.
2. The process of claim 1 wherein the gas-phase reactor is a mechanically stirred vertical gas-phase reactor.
3. The process of claim 2 wherein the gas-phase reactor discharges the product through a dip tube or eductor tube.
4. The process of claim 1 wherein the gas-phase reactor has a bed volume greater than or equal to 35% of the reactor volume.
5. The process of claim 1 wherein the gas-phase reactor is a horizontal gas-phase reactor that is mechanically stirred.
6. The process of claim 1 wherein the activity limiting agent is selected from the group consisting of a carboxylic acid ester, a diether, a poly(alkene glycol), a diol ester, and combinations thereof.
7. The process of claim 1 wherein the activity limiting agent is selected from the group consisting of a laurate, a myristate, a palmitate, a stearate, and an oleate.
8. The process of claim 1 wherein the selectivity control agent is selected from the group consisting of an alkoxysilane, an amine, an ether, a carboxylate, a ketone, an amide, a carbamate, a phosphine, a phosphate, a phosphite, a sulfonate, a sulfone, and a sulfoxide, wherein the alkoxysilane has the general formula SiR m (OR′) 4-m , wherein each R is selected from the group consisting of C 3 -C 12 cycloalkyl, C 3 -C 12 branched alkyl, or C 3 -C 12 cyclic or acyclic amino group, R′ is C 1-4 alkyl, and m is 0, 1, or 2.
9. The process of claim 1 wherein the selectivity control agent is selected from SiR m (OR′) 4-m , wherein R is C 3 -C 12 cycloalkyl, C 3 -C 12 branched alkyl, or C 3 -C 12 cyclic or acyclic amino group, R′ is C 1-4 alkyl, and m is 0,1, or 2.
10. The process of claim 1 wherein the bed bulk density is greater than 160 kg/m 3 .
11. The process of claim 1 wherein the bed bulk density is greater than 192 kg/m 3.
12. The process of claim 1 wherein the bed bulk density is between 128 kg/m 3 to 160 kg/m 3 .
13. The process of claim 1 wherein the bed bulk density is between 128 kg/m 3 to 192 kg/m 3 .
14. The process of claim 1 wherein the gas-phase reactor has a solid holdup larger than 0.21.
15. The process of claim 1 wherein the gas-phase reactor has a solid holdup larger than 0.25.
16. A polymerization process for making polypropylene or propylene copolymer containing C 2 to C 8 comonomers in a gas phase reactor, the process comprising:
polymerizing propylene, optionally with one or more comonomers, in a single flow-pattern gas-phase reactor having a polymer bed with a bed bulk density greater than 128 kg/m 3 , in the presence of a catalyst composition comprising a procatalyst composition and a cocatalyst composition, and a mixed electron donor system, wherein:
a) the mixed electron donor system includes at least a first external electron donor and at least a second external electron donor, the mixed electron donor system comprising at least one selectivity control agent and at least one activity limiting agent, and wherein one of the external electron donors is a carboxylate compound; and
b) the gas-phase reactor having a superficial gas velocity that is less than 10 times the minimum fluidization velocity; and wherein the gas-phase reactor has a solid holdup larger than 0.21 and a bed volume greater than or equal to 35% of the reactor volume.
17. The process of claim 16 wherein the bed bulk density is between 128 kg/m 3 to 192 kg/m 3.
18. The process of claim 16 wherein the gas-phase reactor has a solid holdup larger than 0.25.