Process for the preparation of ethylene polymers using a number of reactors arranged in series
The present invention relates to a process for the preparation of ethylene polymers using a number of reactors arranged in series comprising the steps in which a) ethylene, a diluent, a catalyst, a co-catalyst and optionally comonomers and hydrogen are introduced into a first reactor, b) polymerization of ethylene and optionally comonomers is carried out in the reaction mixture of said first reactor to make ethylene polymers, c) reaction mixture is discharged from said first reactor, d) said reaction mixture and fresh ethylene and optionally comonomers and hydrogen are introduced into the consecutive reactor to make additional ethylene polymers, e) said reaction mixture is discharged from said consecutive reactor and introduced into the further consecutive reactor, if any, with fresh ethylene and optionally comonomers and hydrogen to make additional ethylene polymers, steps c) and d) are repeated until the last reactor of the series, f) reaction mixture is discharged from last reactor of the series and ethylene polymers are recovered, wherein, additional co-catalyst is injected in at least a subsequent reactor of the series. Advantage of the process of the present invention is mainly to decrease catalyst consumption for the same polyethylene production, in other words to increase the productivity. In a most preferred embodiment the process of the present invention is carried out in two loop reactors under slurry conditions.
1. A process for the preparation of ethylene polymers comprising:
introducing ethylene, a diluent, a catalyst, a co-catalyst and optionally comonomers and hydrogen into a first loop reactor to form a first reaction mixture,
polymerizing ethylene and optionally comonomers in the first reaction mixture to form ethylene polymers,
discharging the first reaction mixture from the first loop reactor,
introducing the first reaction mixture and fresh ethylene and optionally comonomers and hydrogen into one or more second reactors to form additional ethylene polymers within a second reaction mixture, wherein the polymerization in all reactors is performed under slurry conditions, and wherein the one or more second reactors are arranged in series and downstream from the first loop reactor and wherein one or more second reactors comprise loop reactors;
discharging the second reaction mixture from the one or more second reactors; and
recovering ethylene polymer, wherein additional co-catalyst is injected in at least one of the second reactors such that the concentration of co-catalyst injected in the at least one of the second reactors, and based on the fresh diluent injected in the at least one of the second reactors, is between 0.1 X and X, wherein X is the concentration of co-catalyst injected in the first loop reactor based on the fresh diluent injected in the first loop reactor, and the production capacity of each reactor is essentially unchanged from a process wherein additional co-catalyst is not injected in at least one of the second reactors;
wherein catalyst is injected only into the first loop reactor, and wherein the catalyst is a metallocene catalyst or a chromium catalysts.
2. The process of claim 1 , wherein the catalyst is the metallocene catalyst.
3. The process of claim 2 , wherein the metallocene catalyst is a transition metal complex comprising a transition metal selected from Group IV of the Periodic Table that is bonded to one or more ligands selected from cyclopentadienyl, indenyl, fluorenyl, or derivatives thereof.
4. The process of claim 2 , wherein the metallocene catalyst is supported on an inert solid silica support.
5. The process of claim 1 , wherein the catalyst is a chromium catalyst that is obtained by deposition of chromium oxide on a silica or alumina support.
6. The process of 1 , wherein the comonomers are introduced into the first loop reactor, and comprise aliphatic C 3 -C 20 alpha-olefins.
7. The process of claim 6 , wherein the comonomers are propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene.
8. The process of claim 6 , wherein the comonomer is hexene, and wherein no hexene is added to the one or more second reactors.
9. The process of claim 1 , wherein the diluent is an aliphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon solvent, an aromatic hydrocarbon solvents.
10. The process of claim 9 , wherein the diluent is halogenated.
11. The process of claim 1 , wherein the diluent is a C 12 or lower saturated hydrocarbon, a C 5 to C 9 saturated alicyclic or aromatic hydrocarbons, or a C 2 to C 6 halogenated hydrocarbon.
12. The process of claim 1 , wherein the diluent is butane, isobutane, pentane, hexane, heptane, cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methyl cyclohexane, isooctane, benzene, toluene, xylene, chloroform, chlorobenzene, tetrachloroethylene, dichloroethane, or trichloroethane.
13. The process of claim 1 , wherein the co-catalyst is a mixture of a non-coordinated Lewis acid and an alkylaluminum.
14. The process of claim 1 , wherein the co-catalyst is an organometallic compound.
15. The process of claim 14 , wherein the catalyst is the metallocene catalyst and the organometallic compound has a general formula AlR 3 , wherein R is an alkyl having 1-16 carbon atoms and each R may be the same or different.
16. The process of claim 14 , wherein the catalyst is a metallocene catalyst and the organometallic compound has a general formula AlR 2 Y, wherein R is an alkyl having 1-16 carbon atoms and each R may be the same or different, and wherein Y is hydrogen or a halogen.
17. The process of claim 1 , wherein the co-catalyst is trimethyl aluminum, triethyl aluminum, di-isobutyl aluminum hydride, tri-isobutyl aluminum, tri-hexyl aluminum, diethyl aluminum chloride, or diethyl aluminum ethoxide.
18. The process of claim 1 , wherein polymerization is carried out at a temperature of from 50° C. to 120° C., and at a pressure of from 20 bars to 100 bars.