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Title:
METHOD FOR FEEDING A FLUID TO A GAS PHASE POLYMERIZATION REACTOR
Document Type and Number:
WIPO Patent Application WO/2018/134007
Kind Code:
A1
Abstract:
A fluid is fed into a polymer bed of a fluidized bed gas phase polymerization reactor by introducing it into the polymer bed through a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein d is the distance of the distributor's discharge end from the wall of the reactor, and D is the diameter of the reactor in the fluidized bed zone.

Inventors:
BALESTRA, Enrico (C/O Basell Poliolefine Italia S.r.l, P.le G. Donegan, 12 Ferrara, 44122, IT)
CAPUTO, Tiziana (C/O Basell Poliolefine Italia S.r.l, P.le G. Donegan, 12 Ferrara, 44122, IT)
COVEZZI, Massimo (C/O Basell Poliolefine Italia S.r.l, P.le G. Donegan, 12 Ferrara, 44122, IT)
DORINI, Maurizio (C/O Basell Poliolefine Italia S.r.l, P.le G. Donegan, 12 Ferrara, 44122, IT)
MAZZUCCO, Antonio (C/O Basell Poliolefine Italia S.r.l, P.le G. Donegan, 12 Ferrara, 44122, IT)
MEI, Gabriele (8280 Sheldon Rd.Channelview, Texas TX, TX 77530, US)
RINALDI, Riccardo (C/O Basell Poliolefine Italia S.r.l, P.le G. Donegan, 12 Ferrara, 44122, IT)
Application Number:
EP2017/082977
Publication Date:
July 26, 2018
Filing Date:
December 15, 2017
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
BASELL POLIOLEFINE ITALIA S.R.L. (Via Pontaccio 10, Milano, 20127, IT)
International Classes:
B01J8/18; B01J8/24; C08F2/00; C08F2/01; C08F10/00
Domestic Patent References:
WO1997004015A11997-02-06
WO2000002929A12000-01-20
WO1998044009A11998-10-08
Foreign References:
EP1083192A12001-03-14
EP0856530A21998-08-05
US6111034A2000-08-29
EP0782587A11997-07-09
EP1012195A12000-06-28
EP0728770A11996-08-28
Attorney, Agent or Firm:
COLUCCI, Giuseppe (Intellectual Property, P.le G. Donegani 12 Ferrara, 44122, IT)
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Claims:
CLAIMS

A method for feeding a fluid into a polymer bed of a fluidized bed gas phase polymerization reactor comprising introducing a controlled and continuous flow rate of the fluid into the polymer bed through a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein d is the distance of the distributor's discharge end from the wall of the reactor, and D is the diameter of the reactor in the fluidized bed zone.

The method according to claim 1 , wherein a head loss is generated through appropriate orifices in the distributor such that a Reynolds number (Re) of from 1 0000 to 700000 is achieved.

The method according to any of the preceding claims, wherein the fluid is an antistatic composition comprising (with respect to the total weight of the antistatic composition) :

(a) from 0.5 to 50 % by weight of a compound of formula R-OH wherein R represents hydrogen or a linear or branched, saturated alkyl group having from 1 to 15 carbon atoms; and

(b) from 50 to 99.5 % by weight of an oligomeric or polymeric organic compound having one or more terminal hydroxyl groups and a viscosity at 40 °C of at least 20 mm2/sec (DIN 51562).

The method according to claim 3, comprising feeding the antistatic composition or individual components thereof to the polymerization reactor in a flow of saturated or unsaturated hydrocarbon having from 2 to 6 carbon atoms.

The method according to any of claims 3 or 4, wherein the compound (a) of formula R-OH is water.

The method according to any of claims 3 to 5, wherein the oligomeric or polymeric organic compound (b) is an alkylene-oxide-derived polymer comprising on average from 1 0 to 200 repeating units— (CH2-CH R-0)-, with R being hydrogen or an alkyl group having from 1 to 6 carbon atoms.

The method according to any of claims 3 to 6, wherein the amount of component (a) in the antistatic composition introduced into the polymerization reactor is from 0.5 to 50 % by weight with respect to the total weight of antistatic composition, and the amount of component (b) in the an- tistatic composition introduced into the polymerization reactor is from 50 to 99.5 % by weight with respect to the total weight of antistatic composition.

The method according to any of claims 1 or 2, wherein the fluid is a catalyst or catalyst component.

The method according to any of the preceding claims, comprising homogenizing inside the distributor the antistatic composition or components and the hydrocarbon.

A fluidized bed gas phase polymerization reactor comprising a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein d is the distance of the distributor's discharge end from the wall of the reactor, and D is the diameter of the reactor in the fluidized bed zone.

A process for the preparation of polyolefins, comprising the step of feeding a fluid into a polymer bed of a fluidized bed gas phase polymerization reactor by introducing a controlled and continuous flow rate of the fluid into the polymer bed through a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein d is the distance of the distributor's discharge end from the wall of the reactor, and D is the diameter of the reactor in the fluidized bed zone.

The process according to claim 1 1 , wherein a Ziegler-Natta catalyst is used comprising:

(i) a solid catalyst component comprising Mg, Ti, an halogen and a first electron donor compound named internal donor,

(ii) an alkylaluminum compound, and

(iii) optionally, a second electron-donor compound named external donor.

Description:
METHOD FOR FEEDING A FLU I D TO A GAS PHASE POLYM ERIZATION REACTOR

FI ELD OF TH E INVENTION [0001 ] The present disclosure pertains to the field of gas phase processes for the polymerization of olefins. More particularly, it relates to a method for feeding a fluid into a fluidized bed gas phase polymerization reactor. It also relates to a process for the polymerization of olefins carried out in the presence of an antistatic compound fed to the polymerization reactor with the method of the invention. BACKGROUND OF THE INVENTION

[0002] Whenever a controlled flow rate of a fluid needs to be fed into the polymer bed of a fluidized bed gas phase polymerization reactor, it is desirable that such fluid contacts the polymer particles as uniformly as possible.

[0003] Examples of fluids to be fed into a fluidized bed gas phase polymerization reactor are those with antifouling and/or antistatic effect.

[0004] The stability of fluidized-bed gas-phase polymerization reactors can be negatively affected by a variety of factors. Among others, the presence of electrostatic charges, hot spots, and low polymer flowability. All those factors may jeopardize the operation of the reactor itself with fouling, sheeting and ultimately blockage of the discharge valve(s), resulting in a shut down. This is true of all types of gas phase polymerization reactors, both in fluidized, fast-fluidized and non-fluidized form (i.e. moving packed beds).

[0005] Antistatic agents are used in processes for the polymerization of olefins to avoid electrostatic charging in order to reduce wall sheeting and formation of polymer agglomerates in the polymerization reactor or in downstream equipment such as degassing and recovery vessels. In the context of olefin polymerization, antistatic agents are also called antifouling agents, polymerization process aids, activity inhibitors, productivity inhibitors or kinetic modifiers. The antistatic agents comprise antistatical- ly-acting compounds which have polar functional groups such as acid or ester groups, amine or amide groups or hydroxyl or ether groups. Examples of antistatically-acting compounds are polysulfone copolymers, polymeric polyamines, polyalcohols, hydroxyesters of polyalcohols, salts of alkylarylsulfonic acids, polysiloxanes, alkoxyamines, polyglycol ethers, etc.

[0006] Another case where a good distribution in a gas phase reactor is required is whenever a liquid co-catalyst has to be fed and a good dispersion will guarantee the required product homogeneity- [0007] It is thus desirable to provide a method for feeding a fluid into the polymer bed of a fluidized bed gas phase polymerization reactor in a manner that such fluid contacts the polymer particles as uniformly as possible.

SUMMARY OF TH E INVENTION

[0008] The present disclosure provides a method for feeding a fluid into a polymer bed of a fluidized bed gas phase polymerization reactor by introducing a controlled and continuous flow rate of the fluid into the polymer bed through a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein

• d is the distance of the distributor's discharge end from the wall of the reactor, and

• D is the diameter of the reactor in the fluidized bed zone. [0009] The present disclosure also provides a fluidized bed gas phase polymerization reactor comprising a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein

• d is the distance of the distributor's discharge end from the wall of the reactor, and · D is the diameter of the reactor in the fluidized bed zone.

[0010] The present disclosure further provides a process for the preparation of polyolefins, said process comprising the step of feeding a fluid into a polymer bed of a fluidized bed gas phase polymerization reactor by introducing a controlled and continuous flow rate of the fluid into the polymer bed through a distributor protruding into the fluidized bed zone of the reactor and terminating with a discharge end positioned so that the following equation is fulfilled: d/D > 0.002 wherein d is the distance of the distributor's discharge end from the wall of the reactor, and

D is the diameter of the reactor in the fluidized bed zone.

BRIEF DESCRI PTION OF THE DRAWINGS

[001 1 ] Figure 1 depicts schematically an illustrative set-up of a fluidized bed gas phase polymerization reactor for carrying out the process for the preparation of polyolefins of the present disclosure, without however restricting the invention to the embodiments illustrated therein.

[0012] Figure 2 shows the inner reactor surface after the polymerization run of Example 1 .

[0013] Figure 3 shows the inner reactor surface after the polymerization run of Comparative Exam- pie 2.

DETAI LED DESCRI PTION OF THE INVENTION

[0014] Fluidized-bed polymerization reactors are reactors in which the polymerization takes place in a bed of polymer particles which is maintained in a fluidized state by feeding in gas at the lower end of a reactor, for example below a gas distribution grid having the function of dispensing the gas flow, and taking off the gas again at its upper end. The reactor gas is then returned to the lower end to the reactor via a recycle line equipped with a compressor and a heat exchanger. The circulated reactor gas is, for example, a mixture of the olefins to be polymerized, inert gases such as nitrogen and/or lower alkanes such as ethane, propane, butane, pentane or hexane and optionally a molecular weight regulator such as hydrogen. According to an embodiment, nitrogen or propane can be used as inert gas, if appropriate in combination with further lower alkanes. The velocity of the reactor gas has to be sufficiently high firstly to fluidize the mixed bed of finely divided polymer present in the tube serving as polymerization zone and secondly to remove the heat of polymerization effectively. The polymerization can also be carried out in a condensed or super-condensed mode, in which part of the circulating re- action gas is cooled to below the dew point and returned to the reactor separately as a liquid and a gas-phase or together as a two-phase mixture in order to make additional use of the enthalpy of vaporization for cooling the reaction gas.

[0015] In some embodiments, the following equations are alternatively fulfilled: d/D > 0.005; d/D > 0.01 0; d/D > 0.015; d/D > 0.020; wherein d is the distance of the distributor's discharge end from the wall of the reactor, and D is the diameter of the reactor in the fluidized bed zone.

[0016] In some embodiments, a head loss is generated through appropriate orifices in the distributor such that a Reynolds number (Re) of from 1 0000 to 700000, or from 20000 to 500000, or from 30000 to 300000 is achieved. [0017] In some embodiments, the fluid is an antistatic compound or composition. In other embodiments, the fluid is a catalyst or catalyst component, such as a cocatalyst.

[0018] In one embodiment, the fluid is an antistatic composition comprising (with respect to the total weight of the antistatic composition) :

(a) from 0.5 to 50 % by weight of a compound of formula R-OH wherein R represents hydrogen or a linear or branched, saturated alkyl group having from 1 to 15 carbon atoms; and (b) from 50 to 99.5 % by weight of an oligomeric or polymeric organic compound having one or more terminal hydroxyl groups and a viscosity at 40 °C of at least 20 mm 2 /sec (DIN 51562).

[0019] In one embodiment, the compound (a) of formula R-OH is water. According to other embodiments, the compound (a) of formula R-OH is an alcohol selected from methanol, ethanol, 1 -propanol, 1 -butanol, 1 -pentanol, 1 -hexanol, 1 -heptanol, 1 -octanol, 1 -nonanol, 1 -decanol, undecan-1 -ol, dodec- an-1 -ol, tridecan-1 -ol, 1 -tetradecanol, pentadecan-1 -ol, isobutanol, isoamyl alcohol, 2-methyl-1 - propanol, phenethyl alcohol, tryptophol, isopropanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, cyclohexanol, tert-butyl alcohol, tert-amyl alcohol, 2-methyl-2-pentanol, 2-methylhexan-2-ol, 2- methylheptan-2-ol, 3-methyl-3-pentanol and 3-methyloctan-3-ol.

[0020] In some embodiments, the oligomeric or polymeric organic compound (b) has a viscosity at 40 °C (DIN 51562) of 30-2000 mm 2 /sec, or of 50-1500 mm 2 /sec, or of 1 00-1 000 mm 2 /sec, or of 150- 500 mm 2 /sec, or of 200-400 mm 2 /sec, or of 250-300 mm 2 /sec, or of 260-285 mm 2 /sec. The preferred viscosity at 40 °C (DIN 51562) of the oligomeric or polymeric organic compound (b) is in the range of 260 to 285 mm 2 /sec.

[0021 ] In some embodiments, the oligomeric or polymeric organic compound (b) is selected from alcohols, polyethers, polyalcohols, hydroxyesters of polyalcohols, polyglycol ethers, polyglycol esters and derivatives thereof.

[0022] In some embodiments, the oligomeric or polymeric organic compound (b) is a polyether and, more specifically, an alkylene-oxide-derived polymer comprising on average from 1 0 to 200 repeating units— (CH2-CHR-O)-, with R being hydrogen or an alkyl group having from 1 to 6 carbon atoms. [0023] In some embodiments, all of terminal groups of the alkylene-oxide-derived polymer are -OH groups.

[0024] In some embodiments, the alkylene-oxide-derived polymer is a random copolymer of ethylene oxide and of other alkylene oxides, and the repeating units— (CH2-CH2-0) n - derived from ethylene oxide to repeating units— (CH 2 -CH R'-0) m - derived from the other alkylene oxides, with R' being an alkyl group having from 1 to 6 carbon atoms, are present in a ratio n : m in the range of from 6 : 1 to 1 : 1 , or in the range of from 5 : 1 to 1 .5 : 1 , or further in the range of from 4 : 1 to 2 : 1 .

[0025] In some embodiments, the alkylene-oxide-derived polymer is a linear polymer of general formula (I)

HO-(CH 2 -CH2-0)n-(CH2-CHR'-0) m -H (I) wherein R' is an alkyl group having from 1 to 6 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms, or a methyl group; n is in the range of from 1 0 to 1 80, or from 20 to 100, or from 30 to 50; m is in the range of from 2 to 120, or from 1 0 to 80, or from 1 0 to 40; n and m denoting the average number of repeating units.

[0026] In some embodiments, alkylene-oxide-derived polymer is a random copolymer of ethylene oxide and propylene oxide.

[0027] In some embodiments, the ethylene oxide/propylene oxide copolymer is a linear ethylene oxide/propylene oxide copolymer of general formula (I I) HO-(CH 2 -CH 2 -0)„-(CH 2 -CH(CH 3 )-0) m -H (I I) wherein n is in the range of from 1 0 to 180, or from 20 to 1 00, or from 30 to 50 and m is in the range of from 2 to 120, or from 10 to 80, or from 1 0 to 40. [0028] Alkylene-oxide-derived polymers for use in the process of the present disclosure can be prepared by reacting ethylene oxide and the other alkylene oxides, such as propylene oxide, with pol- yhydric alcohols like diols, e.g. ethylene glycol, triols, e.g. glycerol, or polyols such as e.g. pentaeryth- ritol. The reaction with diols results in linear polymers. [0029] In some embodiments, the oligomeric or polymeric organic compound (b) is water-soluble. In the contest of the present description, "water-soluble" means soluble in water at room temperature, i.e. at about 23 °C.

[0030] According to embodiments of the disclosure, the amount of antistatic composition intro- duced into the polymerization reactor is from 1 to 5000 ppm per weight, or from 1 0 to 3000 ppm per weight, or from 50 to 1 000 ppm per weight referring to the weight of the prepared polyolefin.

[0031 ] According to embodiments of the disclosure, the amount of component (a) introduced into the polymerization reactor is from 1 to 70 ppm per weight, or from 1 to 50 ppm per weight, or from 2 to 40 ppm per weight, or from 2 to 30 ppm per weight, or from 3 to 30 ppm per weight, or from 3 to 20 ppm per weight referring to the weight of the prepared polyolefin. [0032] According to embodiments of the disclosure, the amount of component (a) in the antistatic composition introduced into the polymerization reactor is from 0.5 to 50 % by weight, or from 3 to 30 % by weight, or from 5 to 15 % by weight with respect to the total weight of antistatic composition. [0033] According to embodiments of the disclosure, the amount of component (b) in the antistatic composition introduced into the polymerization reactor is from 50 to 99.5 % by weight, or from 70 to 97 % by weight, or from 85 to 95 % by weight with respect to the total weight of antistatic composition.

[0034] According to a method of operation, the antistatic composition of the present disclosure can be provided to the polymerization process as a pre-prepared mixture. According to another method of operation, components (a) and (b) of the antistatic composition can be separately provided to the polymerization process.

[0035] In a method of operation, the antistatic composition or individual components thereof can be fed to the polymerization reactor in a flow of saturated or unsaturated hydrocarbon having from 2 to 6 carbon atoms that, according to an embodiment, can be a monomer, such as propylene, and, according to another embodiment, an alkane, such as propane. The monomer and the alkane can be either in liquid or gas form. [0036] According to an embodiment, the antistatic composition or components and the hydrocarbon are homogenized at short distance from the distributor by means of customary mixing/homogenizing/dispersing systems, such as static mixers or atomizers/nebulizers, so to create an emulsion or fog of small droplets of the antistatic dispersed phase into the hydrocarbon continuous phase.

[0037] According to another embodiment, the antistatic composition or components and the hydrocarbon are homogenized inside the distributor, whereby the distributor itself acts as a mixing/homogenizing/dispersing system, such as static mixer or atomizer/nebulizer, so to create an emulsion or fog of small droplets of the antistatic dispersed phase into the hydrocarbon continuous phase.

[0038] According to embodiments in which the components of the antistatic composition are fed separately to the polymer bed, one component is fed through a distributor according to the present disclosure, while the other component can be fed: · upstream or into a catalyst precontacting vessel, i.e. a vessel in which the catalyst components are brought into contact with each other;

• upstream or into a prepolymerization reactor;

• at any other point upstream the polymerization reactor; • suitably distributed in any recirculation flow of the reactor.

[0039] The present disclosure provides a process for the polymerization of olefins, such as 1 - olefins, i.e. hydrocarbons having terminal double bonds, without being restricted thereto. Typical 1 -olefins are linear or branched 1 -alkenes having from 2 to 12 carbon atoms, in particular linear 1 - alkenes having from 2 to 1 0 carbon atoms such as ethylene, propylene, 1 -butene, 1 -pentene, 1 - hexene, 1 -heptene, 1 -octene, 1 -decene or branched 1 -alkenes having from 2 to 1 0 carbon atoms such as 4-methyl-1 -pentene, conjugated and non-conjugated dienes such as 1 ,3-butadiene, 1 ,4-hexadiene or 1 ,7-octadiene or vinyl-aromatic compounds such as styrene or substituted styrene. It is also possi- ble to polymerize mixtures of various 1 -olefins. Olefins that can be polymerized with the process of the present disclosure include those in which the double bond is part of a cyclic structure which can have one or more ring systems. Examples are cyclopentene, norbornene, tetracyclododecene or methyl- norbornene or dienes such as 5-ethylidene-2-norbornene, norbornadiene or ethylnorbornadiene. It is also possible to polymerize mixtures of two or more olefins.

[0040] According to an embodiment, the process can be used for the homopolymerization or co- polymerization of ethylene or for the homopolymerization or copolymerization of propylene. According to an embodiment, comonomers for use in ethylene polymerization are 1 -alkenes having from 3 to 8 carbon atoms such as 1 -butene, 1 -pentene, 1 -hexene and/or 1 -octene in amount of up to 20 wt.% or from 0.01 wt.% to 15 wt.%, or from 0.05 wt.% to 12 wt.%. According to another embodiment, comonomers for use in propylene polymerization are ethylene and/or 1 butene and/or 1 -hexene in amount of up to 40 wt.% or from 0.5 wt.% to 35 wt.%.

[0041 ] The process of the present disclosure allows the preparation of any types of common olefin polymers. According to an embodiment, the prepared olefin polymers can be broad molecular weight olefin polymers and, particularly, multimodal olefin polymers whereby the term multimodal refers to the modality of the molecular weight distribution. As used in the art, and also used herein, multimodal shall include bimodal. Such polymers can be obtained from polymerizing olefins in a cascade of two or more polymerization reactors or in different zones of a multizone reactor under different reaction con- ditions. Thus, the "modality" indicates how many different polymerization conditions were utilized to prepare the polyolefin, independently whether this modality of the molecular weight distribution can be recognized as separated maxima in a gel permeation chromatography (GPC) curve or not. In addition to the molecular weight distribution, the olefin polymer can also have a comonomer distribution. In an embodiment the average comonomer content of polymer chains with a higher molecular weight is higher than the average comonomer content of polymer chains with a lower molecular weight. It is however also possible to employ identical or very similar reaction conditions in all polymerization reactors of the reaction cascade and so prepare narrow molecular weight or monomodal olefin polymers.

[0042] The polymerization of olefins can be carried out using customary olefin polymerization catalysts. That means the polymerization can be carried out using titanium-based Ziegler-Natta-catalysts, Phillips catalysts based on chromium oxide, or single-site catalysts. For the purposes of the present disclosure, single-site catalysts are catalysts based on chemically uniform transition metal coordination compounds. Furthermore, it is also possible to use mixtures of two or more of these catalysts for the polymerization of olefins. Such mixed catalysts may be designated as hybrid catalysts. [0043] According to an embodiment, catalysts for the process of the present disclosure are Ziegler- Natta catalysts comprising:

(i) a solid catalyst component comprising Mg, Ti, an halogen and a first electron donor compound (internal donor),

(ii) an alkylaluminum compound, and

(iii) optionally, a second electron-donor compound (external donor). [0044] Component (i) can be prepared by contacting a magnesium halide, a titanium compound having at least a Ti-halogen bond, and optionally an electron donor compound. The magnesium halide can be MgC in active form which is widely known from the patent literature as a support for Ziegler- Natta catalysts. The titanium compounds can be TiCI 4 or TiCI 3 . Ti-haloalcoholates of formula Ti(OR) n - y Xy, where n is the valence of titanium, y is a number between 1 and n-1 X is halogen and R is a hy- drocarbon radical having from 1 to 1 0 carbon atoms, can also be used.

[0045] Electron donor compounds for preparing Ziegler type catalysts are for example alcohols, glycols, esters, ketones, amines, amides, nitriles, alkoxysilanes and aliphatic ethers. These electron donor compounds can be used alone or in mixtures with other electron donor compounds.

[0046] Other solid catalyst components which may be used are those based on a chromium oxide supported on a refractory oxide, such as silica, and activated by a heat treatment. Catalysts obtainable from those components consist of chromium (VI) trioxide chemically fixed on silica gel. These catalysts are produced under oxidizing conditions by heating the silica gels that have been doped with chromium(l l l)salts (precursor or precatalyst). During this heat treatment, the chromium(ll l) oxidizes to chromium(VI), the chromium(VI) is fixed and the silica gel hydroxyl group is eliminated as water.

[0047] Still other solid catalyst components which may be used are single-site catalysts supported on a carrier, such as metallocene catalysts comprising :

- at least a transition metal compound containing at least one n bond; and

- at least a cocatalyst selected from an alumoxane or a compound able to form an alkylmetallocene cation. [0048] According to embodiments of the disclosure, when the catalyst includes an alkylaluminum compound, such as in Ziegler Natta catalysts, the molar ratio of component (a) to alkylaluminum compound introduced into the polymerization reactor is from 0.05 to 3, or from 0.1 to 2, or from 0.5 to 1 . [0049] The catalysts may be optionally subjected to prepolymerization before being fed to the polymerization reactor. In an embodiment the prepolymerization occurs in a loop reactor. The prepolymerization of the catalyst system may be carried out at a low temperature, for instance in a range of from 0 °C to 60 °C. [0050] According to some embodiments, the fluid catalyst or one or more catalyst components, such as the cocatalyst, are fed with the method of this disclosure.

[0051 ] The process of the present disclosure can be carried in two or more cascade reactors, giving rise to a sequential multistage polymerization process. The fluidized bed gas phase reactor can be preceded and/or followed by one or more liquid-phase and/or gas-phase polymerization reactors. Examples of liquid-phase reactors are loop reactors and continuously stirred tank reactors (CSTR). Examples of gas-phase reactors include fluidized bed reactors, stirred bed reactors and reactors having two interconnected polymerization zones as described in EP 0782587 and EP 10121 95. [0052] For instance, a fluidized bed reactor can be used to prepare a first polymer component, which is successively fed to a gas-phase reactor having two interconnected polymerization zones to prepare a second and a third polymer component. Or a first fluidized bed reactor can be used to prepare a first polymer component, which is successively fed to a second fluidized bed reactor to prepare a second polymer component and then to a third fluidized bed reactor to prepare a third polymer com- ponent. Accordingly, an olefin polymer endowed with a multi-modal molecular weight distribution can be obtained, as well as an olefin copolymer comprising two or more components having a different comonomer content.

[0053] Gas-phase polymerization reactors other than fluidized bed gas-phase reactors can be, for example, horizontally or vertically stirred reactor or multizone circulating reactors.

[0054] Multizone circulating reactors are gas-phase reactors in which two polymerization zones are linked to one another and the polymer is passed alternately a plurality of times through these two zones. Such reactors are, for example, described in WO 97/04015 A1 and WO 00/02929 A1 and have two interconnected polymerization zones, a riser, in which the growing polymer particles flow upward under fast fluidization or transport conditions and a downcomer, in which the growing polymer particles flow in a densified form under the action of gravity. The polymer particles leaving the riser enter the downcomer and the polymer particles leaving the downcomer are reintroduced into the riser, thus establishing a circulation of polymer between the two polymerization zones and the polymer is passed alternately a plurality of times through these two zones. It is further also possible to operate the two polymerization zones of one multizone circulating reactor with different polymerization condi- tions by establishing different polymerization conditions in its riser and its downcomer. For this purpose, the gas mixture leaving the riser and entraining the polymer particles can be partially or totally prevented from entering the downcomer. This can for example be achieved by feeding a barrier fluid in form of a gas and/or a liquid mixture into the downcomer, in the upper part thereof according to an embodiment. The barrier fluid should have an appropriate composition, different from that of the gas mixture present in the riser. The amount of added barrier fluid can be adjusted in a way that an upward flow of gas countercurrent to the flow of the polymer particles is generated, particularly at the top thereof, acting as a barrier to the gas mixture entrained among the particles coming from the riser. In this manner it is possible to obtain two different gas composition zones in one multizone circulating reactor. Furthermore it is also possible to introduce make-up monomers, comonomers, molecular weight regulator such as hydrogen and/or inert fluids at any point of the downcomer, below the barrier feeding point according to an embodiment. Thus, it is also easily possible to create varying monomer, comonomer and hydrogen concentrations along the downcomer, resulting in a further differentiation of the polymerization conditions.

[0055] In a gas-phase polymerization process, the solid polymers are obtained from a gas-phase of the monomer or the monomers. Such gas-phase polymerizations may be carried out at pressures of from 0.1 to 20 MPa, or from 0.5 to 1 0 M Pa, or from 1 .0 to 5 M Pa and polymerization temperatures from 40 to 150 °C or from 65 to 125 °C.

[0056] A fluidized bed gas phase polymerization reactor, representing an embodiment of the disclosure, will now be described in detail with reference to the enclosed Figure 1 , which is a diagrammatic representation and has to be considered illustrative and not limitative of the scope of the invention.

[0057] In such embodiment, schematically, a solid catalyst component 1 , a stream 2 containing the cocatalyst and an external donor compound, optionally in the presence of propylene, are fed to a pre- contacting vessel 3 together with a diluent, such as propane. [0058] The obtained catalyst system is continuously fed via line 4 to a loop prepolymerization reactor 5, and simultaneously liquid propylene is fed to the reactor 5 via line 6, optionally together with an alkane, such as propane.

[0059] The prepolymerized catalyst system discharged from the loop reactor 5 is fed via line 7 to a fluidized bed reactor 8.

[0060] The fluidized bed reactor 8 of Fig. 1 comprises a fluidized bed 9 of growing polymer particles, a fluidization plate 1 0 and a velocity reduction zone 1 1 . The velocity reduction zone 1 1 is generally of increased diameter compared to the diameter of the fluidized bed portion of the reactor. The gaseous stream leaving the top of the velocity reduction zone 1 1 is transferred via the recycle line 12 to a compressor 13 and then to a heat exchanger 14. The recycle line 12 is equipped with a line 15 for feeding propylene, hydrogen, inert gases and, optionally comonomers. Passing through the heat exchanger 14, the gaseous stream is cooled and then fed to the bottom of the fluidized bed reactor 8. In this way the upwardly flowing gas continuously maintains the bed of polymer particles in fluidization conditions.

[0061 ] The polymer obtained reactor 8 is discharged from the lower part of the fluidized bed 9 and is fed via line 1 6 to a solid/gas separator 17. Said gaseous mixture is fed back to the recycle line 1 2 through line 18, while the separated polymer is fed via line 1 9 to the next sections of the plant. [0062] The antistatic composition can be added into the fluidized bed reactor 8 via line 20 through a distributor 21 protruding into the fluidized bed zone 9 of the reactor. Additionally, it can be added via an injection point 22 on line 7 exiting from the prepolymerization reactor 5 and entering the fluidized bed reactor 8. [0063] According to an embodiment, the gas-phase polymerization processes according to the present disclosure are carried out in the presence of an alkane having from 3 to 5 carbon atoms as polymerization diluent, e.g. in the presence of propane.

[0064] The process of the present disclosure provides a possibility for preparing an olefin polymer by gas-phase polymerization in a polymerization reactor in which the formation of polymer agglomerates in the polymerization reactors and fluctuations in the fluid-dynamics of the reactor are prevented or considerably reduced. Because of the reduced electrostatics, the tendency of the olefin polymer particles to stick to the reactor walls is reduced. This does not only reduce the risk of forming chunks or wall sheeting, which mostly leads to an unavoidable shut-down of the polymerization reactor be- cause of plugging the discharge line, but also improves the fluid-dynamics of the reactor and avoids their fluctuations.

[0065] Using an antistatic composition does not only result in a process for the polymerization of olefins which is simple to carry out, but the polymerization process has also a good operability. That means that the tendency for forming polymer deposits on the rector wall, i.e. reactor fouling, for forming lumps and for forming fines, i.e. for forming very small polyolefin particles, is reduced. Moreover, the activity of the catalyst is improved or at least not impaired and the product properties of the prepared polyolefins are not deteriorated. EXAM PLES

[0066] The following examples are given to illustrate the present invention without any limiting purpose.

Test Methods Melt flow rate (M FR "L")

[0067] Determined according to ISO 1 133 (230 2.16 Kg) Ethylene content in copolymers

[0068] The content of ethylene comonomer was determined by infrared spectroscopy by collecting the I R spectrum of the sample vs. an air background with a Fourier Transform Infrared spectrometer (FTIR). The instrument data acquisition parameters were:

- purge time: 30 seconds minimum

- collect time: 3 minutes minimum - apodization: Happ-Genzel

- resolution: 2 cm -1 .

[0069] Sample Preparation - Using a hydraulic press, a thick sheet was obtained by pressing about g 1 of sample between two aluminum foils. A small portion was cut from this sheet to mold a film.

Recommended film thickness ranges between 0.02 and 0.05 cm (8 - 20 mils). Pressing temperature was 1 80±1 0 °C (356 °F) and about 1 0 kg/cm2 (142.2 PSI) pressure for about one minute. The pressure was released, the sample removed from the press and cooled to room temperature. [0070] The spectrum of pressed film sample was recorded in absorbance vs. wavenumbers (cm- 1 ). The following measurements were used to calculate ethylene content:

- Area (At) of the combination absorption bands between 4482 and 3950 cm -1 , used for spectrometric normalization of film thickness;

- Area (AC2) of the absorption band between 750-700 cm -1 after two proper consecutive spectroscopic subtractions of an isotactic non-additivated polypropylene spectrum and then of a reference spectrum of an ethylene-propylene random copolymer in the range 800-690 cm -1 ; - Height (DC4) of the absorption band at 769 cm -1 (maximum value), after two proper consecutive spectroscopic subtractions of an isotactic non-additivated polypropylene spectrum and then of a reference spectrum of an ethylene-propylene random copolymer in the range 800-690 cm -1 .

[0071 ] In order to calculate the ethylene content, a calibration straight line for ethylene obtained by using samples of known amount of ethylene is needed and was obtained by plotting AC2/At versus ethylene molar percent (%C2m). The slope GC2 was calculated from a linear regression. [0072] The spectra of the unknown samples were recorded and then (At), (AC2) and (DC4) of the unknown sample calculated. The ethylene content by weight was obtained from the ethylene content (% molar fraction C2m) of the sample calculated as follows:

[0073] Determined as follows: 2.5 g of polymer and 250 ml of xylene were introduced in a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature was raised in 30 minutes up to the boiling point of the solvent. The clear solution so obtained was then kept under reflux and stirring for further 30 minutes. The closed flask was then kept in thermostatic water bath at 25 ° C for 30 minutes. The so formed solid was filtered on quick filtering paper. 1 00 ml of the filtered liquid was poured in a previously weighed aluminum container, which was heated on a heating plate under nitrogen flow, to remove the solvent by evaporation. The container was then kept in an oven at 80 ° C under vacuum until constant weight was obtained. The weight percentage of polymer soluble in xylene at room temperature was then calculated.

Example 1

Preparation of the Zieqler-Natta solid catalyst component

[0074] An initial amount of microspheroidal MgCl 2 '2.8C 2 H 5 OH adduct was prepared according to the method described in Example 2 of WO98/44009, but operating on larger scale. The so-obtained adduct was then partially dealcoholated in a nitrogen flow until the alcohol content reached the value of 50%wt based on the total weight of the adduct.

[0075] 300 ml of TiCI4 were introduced at room temperature under nitrogen atmosphere into a 500 ml round bottom flask, equipped with mechanical stirrer, cooler and thermometer. After cooling to 0 °C, while stirring, diisobutylphthalate (internal donor) and 9.0 g of the adduct prepared as described above were sequentially added into the flask. The amount of internal donor added was such as to meet a Mg/donor molar ratio of 8. The temperature was raised to 100 °C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100 °C. After the supernatant was removed, additional fresh TiCI4 was added to reach the initial liquid volume again. The mixture was then heated at 120 °C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60 °C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed. Catalyst Activation and Prepolymerization

[0076] Before introducing it into the polymerization reactors, the solid catalyst component prepared as described above was contacted with aluminum-triethyl (TEAL) and with dicyclopentyl- dimethoxysilane (donor D) under the conditions reported in Table 1 .

[0077] The activated catalyst discharged from the activation vessel was continuously fed, together with liquid propylene, to a prepolymerization loop reactor operated at a temperature of 20 °C and a residence time of 7 minutes.

Polymerization

[0078] The polymerization run was conducted in continuous mode in a fluidized bed gas-phase reactor as illustrated in Figure 1 , having a diameter of 40 cm in the fluidized bed zone. The prepoly- merized catalyst was discharged from the prepolymerization reactor and was continuously fed to a fluidized bed gas-phase reactor where an ethylene-propylene copolymer was prepared. Liquid propylene, ethylene and hydrogen as molecular weight regulator were fed to reactor 8 via line 15 into the recycle line 12. [0079] An antistatic composition comprising 7 %w of water and 93 %w of Polyglykol PE-K 270 commercialized by Clariant was fed into the polymer bed partly through an injection point 22 on line 7 exiting from the prepolymerization reactor 5 and entering the fluidized bed reactor 8 and partly via a distributor 21 protruding into fluidized bed zone 9 and terminating with a discharge end positioned 1 0 cm from the wall of the reactor. The flow rate of the antistatic composition feed was such as to obtain in the polymer the amounts of antistatic indicated in Table 1 and was split 50/50 between the two injection points. The gas phase (propylene, ethylene and hydrogen) was continuously analyzed via gas- chromatography. At the end of the run the powder was discharged and dried under a nitrogen flow.

[0080] The main polymerization conditions and polymer features are reported in Table 1 together with the effect of the antistatic composition.

[0081 ] The antistatic composition proved to be effective. Also, visual inspection of the reactor surface (Figure 2) showed that its wall were clean, namely there was no formation of sheeting or adhesion of polymer particles. The addition of the antistatic composition ensured a very stable operation of the plant for the duration of the trial, as evidenced by the absence of problems at the reactor discharge. Also, the presence of the antistatic agent did not negatively affect the catalyst activity.

Example 2C (comparative)

Preparation of the Zieqler-Natta solid catalyst component [0082] Prepared in accordance with example 1 of EP 728770 with the difference that the diameter of the spherical adduct particles was 60 micron.

Catalyst Activation, Prepolymerization and Polymerization

[0083] Example 1 was repeated with slight condition differences indicated in Table 1 and with the additional difference that the antistatic composition was fed into the polymer bed only via the injection point 22 on line 7 exiting from the prepolymerization reactor 5. I n this case, the antistatic effect was lower, as reported in Table 1 below. Visual inspection of the reactor surface (Figure 3) showed that it was found severely fouled.

Table 1

Notes: C = ethylene; C3 " = propylene; H2 = hydrogen; Split = amount of polymer prepared in the con- cerned reactor referred to the total weight; Mileage = amount of obtained polymer per amount of catalyst fed to the polymerization.