WO2006063771A1 - Process for polymerising olefins in the presence of an olefin polymerisation catalyst - Google Patents
Process for polymerising olefins in the presence of an olefin polymerisation catalyst Download PDFInfo
- Publication number
- WO2006063771A1 WO2006063771A1 PCT/EP2005/013315 EP2005013315W WO2006063771A1 WO 2006063771 A1 WO2006063771 A1 WO 2006063771A1 EP 2005013315 W EP2005013315 W EP 2005013315W WO 2006063771 A1 WO2006063771 A1 WO 2006063771A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- slurry
- oil
- reactor
- process according
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/919—Catalyst injection technique in addition polymerization processes
Definitions
- the present invention deals with a process of producing olefin polymers in the presence of an olefin polymerisation catalyst. More specifically, the present invention deals with a method of transferring a solid polymerisation catalyst component into the polymerisation reactor. In particular, the solid catalyst component can be metered into the reactor with good accuracy without damaging the properties of the catalyst.
- WO 9216747 discloses a device and a method for metering a viscous mixture of a wax and a polymerisation catalyst into the polymerisation reactor by using a valveless piston pump. It was disclosed that the catalyst - wax mixture having a viscosity of from 0.1 to 500000 mPa-s could be used. However, it was reported that the catalyst was mixed with a solution of polyethylene wax and liquid poly-alpha-olefm, where the viscosity of the polyethylene wax - poly-alpha-olef ⁇ n mixture was 4500 mPa-s in the feed conditions.
- WO 00/47638 discloses a method for polymerising olefins in the presence of a preactivated catalyst.
- the catalyst was mixed with oil and wax and metered into the polymerisation reactor by using a device disclosed in WO 9216747.
- the viscosity of the mixture was from 1 to 15 Pas, preferably from 4 to 10 Pas.
- DE 248634 discloses a valveless piston pump capable for pumping viscous materials.
- WO 01/05845 discloses a method for polymerising olefins in a fluidised bed gas phase reactor, where a solid catalyst component was mixed with oil having a viscosity of at least 50 mPa-s, preferably greater than 100 mPa-s but no greater than 5000 mPa-s.
- the catalyst slurry was mixed with aluminium alkyl compounds and passed through a static mixer, after which it was introduced into a fluidised bed polymerisation reactor.
- EP 459218 discloses a shot-injector type of catalyst feeder, where catalyst slurry is allowed to settle so that the catalyst fills a bore of a feeder valve. When the valve turns the shot of settled catalyst is injected into the polymerisation reactor.
- Solid catalyst components having small particle size, low density or high porosity have a tendency of settling slowly in a diluent. Therefore, if such catalysts are fed by using shot injector type of feeders as disclosed in EP 459218, the feed capacity is limited due to the low content of solid catalyst in the feed shots. This problem can be solved by mixing the catalyst into a viscous wax mixture, but the use of additional and viscous components requires special equipment.
- One aspect of the present invention is to provide a polymerization process comprising the steps of: (i) forming a catalyst slurry in a catalyst feed vessel comprising a. an oil, and b. a solid polymerization catalyst component;
- the process of the present invention comprises a process for olefin polymerisation, in which process at least one olefin monomer is polymerised in a polymerisation reactor in the presence of an olefin polymerisation catalyst.
- Said olefin polymerisation catalyst comprises at least a solid catalyst component comprising at least one transition metal compound.
- said solid catalyst component is suspended in oil to form catalyst slurry.
- Said catalyst slurry is maintained in homogeneous condition in a catalyst slurry vessel. A small portion of said slurry is continuously withdrawn from said catalyst slurry vessel and metered by using a catalyst slurry metering pump and introduced into a polymerisation reactor with a predefined rate.
- the invention allows transferring different solid catalyst components whose particle size may vary over a wide range. Also, different types of catalysts supported on different types of supports may be used in the present invention. The invention is also suitable for transferring solid unsupported catalysts into a polymerisation reactor.
- the method of the invention is useful in feeding catalysts having a small particle size into the polymerisation reactor.
- the catalysts can be fed into the polymerisation reactor with a high accuracy and no capacity problems, e.g. due to poor settling, are observed.
- the polymerisation can be conducted in stable conditions without fluctuations in the production rate due to inconsistent catalyst feed.
- FIG 1 shows one arrangement to feed catalyst according to the present invention.
- the oil is transferred from the oil drums into the oil storage tank V-001 by using the oil pump P-
- Nitrogen lines are connected to both the oil drum and the oil storage tank to keep the oil under inert atmosphere.
- the oil is transferred from the oil storage tank into the catalyst mix tank V-002 by means of the oil pump P-001.
- the catalyst is transferred from the catalyst unloading station either in dry form or as slurry into the catalyst mix tank V-
- Nitrogen can also be lead into the catalyst unloading station and the catalyst mix tank.
- the catalyst mix tank V-002 is equipped with an agitator to keep the slurry as homogeneous and a cooling/heating jacket to keep the temperature constant.
- the catalyst slurry is continuously metered from the catalyst mix tank into the prepolymerisation reactor by using the catalyst feed pump P-002.
- the catalyst slurry is combined with the diluent stream and transferred into the reactor.
- the transport barrel is first tumbled in a drum tumbler in three dimensions. This ensures that no cake of catalyst shall remain in the transport barrel. This kind of tumbling is more effective than rolling.
- the barrel When the barrel has been properly tumbled, e.g. for about 30 minutes to two hours, it is connected to a pipeline, through which the catalyst slurry is taken into the catalyst mix tank by using pressurised oil.
- the advantage is then that it is not necessary to carry the barrel to a high level where the catalyst feeder may be located, but the operations may be carried out at a ground level.
- FIG. 2 shows a test arrangement that was used to test the functionality of the present concept.
- the arrangement includes a catalyst mix tank, which is equipped with an agitator and a cooling/heating jacket.
- the catalyst slurry is prepared into the mix tank and recycled by using the catalyst feed pump from the bottom of the catalyst mix tank to an opening at the upper part of the mix tank.
- the solid catalyst component is suspended in oil to produce catalyst slurry.
- the catalyst slurry is maintained in homogeneous state and a portion of the slurry is continuously withdrawn from the catalyst slurry vessel and introduced into a polymerisation reactor.
- the catalyst slurry is contacted with an activator and/or an electron donor before it is introduced into the polymerisation reactor.
- the catalyst may be of Ziegler-Natta type.
- it may contain a magnesium compound and a titanium compound supported on an inorganic oxide carrier, as disclosed in EP 688794, WO 91/16361, WO 93/13141, WO 94/14857, WO 99/51646 and WO ⁇ I / ⁇ OT ⁇ ⁇ j TM ⁇ 7 ⁇ iw it ma ⁇ ⁇ ion rnntnin a titanium nnmnound suDDorted on masnesium halide, as disclosed in WO 03/000756, WO 03/000757, WO 03/000754, WO 92/19653, WO 93/07182, WO 97/36939 and WO 99/58584.
- the catalyst may also be unsupported comprising particles of solid titanium trichloride, optionally containing additional components, such as aluminium trichloride.
- the catalyst may also be a chromium catalyst, typically supported on silica.
- Such catalysts are disclosed, among others, in WO 99/52951 and WO 97/27225.
- the catalyst may be a metallocene catalyst. Often such catalysts are supported, preferably on an inorganic oxide carrier, as disclosed in WO 95/12622, WO 96/32423, WO 98/32776 and WO 00/22011. However, the catalyst may also be prepared by forming the support from alumoxane and incorporating the metallocene compound on the alumoxane. Such a method of preparing solid metallocene catalyst components is disclosed in WO 03/051934.
- the solid catalyst component may comprise polymer. Thus, it may have been prepolymerised to produce a minor amount of polymer on the solid catalyst component, for instance from 0.01 to 50 grams of polymer per gram of the solid component.
- the monomer used for prepolymerisation may be the same as used in the polymerisation reactor, or it may be different therefrom.
- the solid catalyst component may be delivered as a dry powder, or it be delivered in oil slurry. If the catalyst is delivered as slurry, the oil used in the slurry is preferably the same as or at least similar to the oil used in the catalyst feed.
- the concentration of the solid catalyst component in the transport slurry may be up to 450 kg/m 3 .
- the concentration of the solid catalyst component can be selected freely so that the desired catalyst feed rate is conveniently obtained. However, said concentration must not be too high, as otherwise it may be difficult to maintain stable slurry. On the other hand, too low concentration may result in using excessive amount of oil, which may cause problems in increasing the level of extractable matters in the final polymer product. It has been found that suitable catalyst concentration is from 50 to 500 kg/m 3 , preferably from 100 to 400 kg/m 3 and in particular from 150 to 300 kg/m 3 , based on the volume of the slurry. on
- the oil to be used must be inert towards the catalyst. This means that it must not contain components having tendency to react with the catalyst, such as groups containing atoms selected from oxygen, sulphur, nitrogen, chlorine, fluorine, bromine, iodine and so on. Also groups containing double bonds or triple bonds should be avoided. Especially the presence of compounds like water, alcohols, organic sulphides, ketones, carbon monoxide, carbon dioxide and acetylenic compounds should be avoided.
- the oil is hydrocarbon oil or silicon oil, more preferably hydrocarbon oil, containing less than 100 parts per million (ppm) of compounds containing said groups. More preferably, the content of such compounds is less than 50 ppm and in particular less than 10 ppm.
- suitable oils are mineral oils and synthetic oils comprising essentially of hydrocarbons containing from about 15 to about 50 carbon atoms; Synton PAO 100TM, which is a synthetic oil supplied by Crompton Petroleum Additives; Shell Cassida HF 15TM, Shell Cassida HF 32TM, Shell Cassida 46TM, Shell Cassida HF 68TM and Shell Cassida HF 100TM, which are synthetic oils supplied by Shell; Drakeol 35TM, which is a synthetic oil supplied by Penreco; Ondina 68TM, which is a mineral oil supplied by Shell and Primol 352TM, which is supplied by ExxonMobil.
- the viscosity of the oil should be such that stable slurry is obtained and the tendency of the catalyst particles to settle is minimal. Therefore, the oil should not have a too low viscosity.
- the slurry should be readily transportable into the polymerisation reactor. A very high viscosity causes problems in catalyst handling, as highly viscous fluids need special operations in their handling. Moreover, the viscous wax remaining in the polymer product after the polymerisation may have a negative effect on the product properties.
- the dynamic viscosity of the oil is from 20 to 3000 mPa-s at the operating temperature of the catalyst feed vessel.
- the dynamic viscosity is from 20 to 1500 mPa-s, more preferably from 30 to 990 mPa-s, when measured at the operating temperature of the feed vessel.
- the viscosity of the oil should be sufficiently high to allow the operation of the feed pump.
- the oil should lubricate the piston of the catalyst feed pump, to allow its smooth operation.
- the catalyst slurry may contain additional components, such as activators, electron donors, modifiers, antistatic agents and so on. If such components are used, they may be combined with the catalyst slurry in the slurry vessel, or they may be combined with the catalyst slurry stream to be introduced into the polymerisation reactor, or they may be introduced directly into the polymerisation reactor without precontacting them with the catalyst slurry.
- additional components such as activators, electron donors, modifiers, antistatic agents and so on. If such components are used, they may be combined with the catalyst slurry in the slurry vessel, or they may be combined with the catalyst slurry stream to be introduced into the polymerisation reactor, or they may be introduced directly into the polymerisation reactor without precontacting them with the catalyst slurry.
- organometal compounds such as the organoaluminium compounds and in specific the aluminium alkyls.
- organoaluminium compounds such as the organoaluminium compounds and in specific the aluminium alkyls.
- examples of such preferred compounds are trimethylaluminium, triethylaluminium, tri-isobutylaluminium, tri-n-hexylaluminium, tri-n-octylaluminum and isoprenyl aluminium.
- methylalumoxane tri-isobutylalumoxane, hexa-isobutylalumoxane and other alumoxanes
- dimethylaluminium chloride diethylaluminium chloride
- methylaluminium sesquichloride methylaluminium sesquichloride
- ethylaluminium sesquichloride diethyl zinc and triethyl boron.
- ethers examples include ethers, esters, ketones, alcohols, carboxylic acids, silicon ethers, imides, amides and amines.
- Drag reducing agents are typically soluble polymers of high alpha-olefins, like C 6 to C 15 alpha-olefins, preferably C 8 to C 13 alpha-olefms, and their mixtures. They may comprise a minor amount of comonomer units derived from other olefins as well. It is important, however, that the drag reducing agent is soluble in the oil.
- the drag reducing agent is used in an amount of 0.1 to 1000 ppm, preferably 0.5 to 100 ppm and more preferably 1 to 50 ppm by weight of the catalyst slurry.
- Drag reducing agents are available on the market and they are supplied, among others, by M-I Production Chemicals and Conocon.
- the former supplies a product with a trade name NECADD 447TM, which has been found to be useful in preventing the settling of the catalyst particles.
- the drag reducing agent typically has a weight average molecular weight of at least 250000 g/mol, preferably at least 500000 g/mol and more preferably at least 800000 g/mol.
- the drag reducing agent has a weight average molecular weight of more than 1000000 g/mol.
- the high molecular weight corresponds to a high inherent viscosity.
- the drag reducing agent has an inherent viscosity of at least 10 dl/g measured using a Cannon-Ubbelohde four bulb shear dilution viscometer (O.lg polymer/100 ml toluene at 25 0 C).
- the drag reducing agent when a drag reducing agent is added into the catalyst slurry, it delays the settling process and prevents the catalyst particles from agglomerating. For this reason, the drag reducing agent can be advantageously used to improve the transport and storage stability of the slurry. If the catalyst were transported and stored in slurry, the drag reducing agent may be added into the slurry when it is loaded into transportation drums. In this way sedimentation of the catalyst during transport and storage can be avoided. The addition of the drag reducing agent is especially useful when transporting, storing and feeding solid catalyst components having a small particle size. Also it has been surprisingly found that the drag reducing agent, if used in the amounts disclosed above, has no, or a negligible effect on the viscosity of the oil and no negative effect on the handling properties of the slurry.
- the process of introducing the catalyst into the polymerisation reactor comprises the following steps: (i) forming a catalyst slurry comprising a. an oil, and b. a solid catalyst component
- the catalyst slurry may be formed in any method known in the art. According to a preferred method, the solid catalyst component is introduced into the oil under agitation.
- the slurry may be prepared in the catalyst feed vessel or it may be prepared in advance and then transferred into the catalyst feed vessel. Further, the solid catalyst component may also be delivered into the feed vessel as concentrated slurry, which may then be diluted with oil in the feed vessel.
- the homogeneous slurry is maintained by agitation.
- the agitation can be obtained by circulating the slurry by using a circulation pump and pipes connecting the pump to the catalyst feed vessel.
- the catalyst feed vessel is equipped with an agitator, which keeps the slurry within the feed vessel in motion.
- the catalyst feed vessel is equipped with an agitator.
- the elements of the agitator should be chosen so that uniform stirring in the whole volume of the catalyst feed vessel is obtained and no dead spots where the catalyst could settle exist.
- stirrer elements such as anchor type elements and axial and radial impellers are well known in the art and a person skilled in the art can choose a suitable combination for each geometry of the catalyst feed vessel.
- the catalyst feed vessel may also be equipped with baffles, which are known in the art to further improve the stirring.
- the revolution speed of the agitator N should be selected so that N > Nj 3 , where N j5 is the just suspended speed and which can be calculated from correlations available in the art, for instance in Zwietering Th. N., "Suspending of solids particles in liquid by agitators", Chem Eng Sci, VoI 8, pp 244...254, 1958.
- the temperature of the slurry within the catalyst feed vessel is not critical. However, too low and too high temperatures should be avoided, as otherwise the viscosity of the slurry might either become too high so that it cannot be conveniently handled in the process or too low so that the particles tend to settle.
- the temperature may be selected from the range of from -30 0 C to + 80 0 C, preferably from 0 °C to 60 0 C. It is preferred to equip the catalyst feed vessel with a heating/cooling jacket so that the temperature in the vessel can be maintained within the desired level. Especially, the temperature of the slurry should be adjusted so that the viscosity of the oil would be within the desired limits. Moreover, temperature variations should be avoided; they cause variations in the density of the slurry. If the density of the slurry varies, then the catalyst feed rate shall vary accordingly and this could cause fluctuations in the polymerisation process.
- the pressure within the catalyst feed vessel is not critical, either. It can be selected within the operating range of the process equipment. Especially, it should be selected so that the pumps can be operated without problems. It is desired that the pressure in the catalyst feed vessel is higher than the atmospheric pressure to minimise the eventual leaks of air and/or moisture into the catalyst feed vessel.
- the catalyst feed vessel must be maintained in inert atmosphere. Especially, the presence of oxygen and moisture should be avoided. Therefore, all the connections to the vessel, such as pipe joints and agitator shaft bearing need to be carefully designed to eliminate the leaks from the atmosphere. Also, the process chemicals, such as the lubricating oil for the bearings, needs to be selected so that they do not contain components that are harmful for the catalyst, or alternatively, their carryover into the catalyst feed vessel needs to be prevented. It is especially preferred to use as the lubricating oil the same oil that is used as a diluent in the catalyst slurry.
- the gas phase in the catalyst feed vessel should preferably consist of nitrogen, argon and similar inert gases, or their mixtures. Also, the catalyst feed vessel should be equipped with possibility to flush the vessel with inert gas, preferably with nitrogen. .
- a portion of the homogeneous slurry is continuously withdrawn from the feed vessel and introduced into a polymerisation reactor.
- the slurry is metered into the reactor by using a metering pump.
- the metering pump may be any pump that is capable of metering slurries with the specified viscosity in the required amount.
- One pump that has been found as especially useful in the process of the invention is a valveless piston pump. Examples of such pumps and their use are given in WO 92/16747, WO 00/47638 and DE 248634.
- the catalyst feed line may be equipped with a catalyst flow meter.
- Flow meters suitable for measuring the catalyst feed rate are disclosed in PCT patent application PCT/EP03/15031, or are commercially available, among others, from Oxford Instruments.
- Such a flow meter may also be used as a part of a control loop to control the catalyst feed rate. For example, a signal from the flow meter is compared with a predetermined set value, and the signal to the metering pump is adjusted based on the difference.
- the activator and/or electron donor When used, it may be mixed with the catalyst slurry in different ways.
- One alternative is to introduce the activator and/or electron donor to the catalyst feed vessel.
- Another alternative is to combine the activator and/or the electron donor with the catalyst slurry in the catalyst feed line.
- a third alternative is to introduce the activator and/or the electron donor directly into the polymerisation reactor. In addition, in some cases it may be beneficial to use a combination of two of the three methods discussed above or a combination of all of them.
- the proposed method of feeding the catalyst is especially useful for catalysts having high activity.
- the catalysts suitable for being fed using the method of the invention preferably have a productivity in the polymerisation step of more than 3 kg polymer/g catalyst, more preferably of more than 5 kg/g catalyst, and especially preferably of more than 10 kg/ g catalyst and in particular more than 15 kg/g catalyst.
- the activity of the catalyst is high, the feed rate of the catalyst slurry can be maintained at a low level. Then the residues of the oil in the final polymer are smaller.
- Another aspect of the present invention is to provide a polymerization process comprising the steps of: (i) forming a catalyst slurry in a catalyst feed vessel comprising a. an oil, and b. a solid polymerization catalyst component;
- the polymerisation may be conducted in any method that is known in the art, such as in slurry, solution or gas phase.
- the method of the invention does not cause notable attrition and disintegration of the catalyst particles during the catalyst feed, it is particularly suitable for particle forming processes, such as slurry or gas phase.
- the polymerisation stage is preceded by a prepolymerisation stage.
- prepolymerisation a small amount of an olefin, preferably from 0.1 to 500 grams of olefin per one gram catalyst is polymerised.
- the prepolymerisation takes place at a lower temperature and/or lower monomer concentration than the actual polymerisation.
- the prepolymerisation is conducted from 0 to 70 °C, preferably from 10 to 60 0 C.
- the monomer used in the prepolymerisation is the same that is used in the subsequent polymerisation stage(s). It is also possible to feed more than one monomer into the prepolymerisation stage. Description of prepolymerisation can be found in e.g. WO 96/18662, WO 03/037941, GB 1532332, EP 517183, EP 560312 and EP 99774.
- alpha-olefins of from 2 to 20 carbon atoms can be polymerised. Especially ethylene and/or propylene, optionally together with higher alpha- olefins are polymerised.
- the polymers obtained from the process include all the olefin polymers and copolymers known in the art, such as high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), polypropylene homopolymers, random copolymers of propylene and ethylene or propylene and higher alpha-olefins, heterophasic copolymers of propylene and ethylene, poly-1- butene and poly-4-methyl-l-pentene.
- higher alpha-olefins are used as comonomers, they are preferably selected from the group consisting of 1-butene, 1-hexene, 4-methyl-l- pentene, 1-octene and 1-decene.
- polymerisation stage it is within the scope of the invention to conduct the polymerisation in at least one polymerisation stage. It is also known in the art to polymerise in at least two polymerisation stages to produce bimodal polyolefins, such as bimodal polyethylene and bimodal polypropylene, as disclosed in WO 92/12182, EP 22376, EP 713888 and WO 98/58975. Further, multistage polymerisation may be used to produce heterophasic propylene copolymers, as disclosed in WO 98/58976. It is to be understood that the present invention is not limited to any specific number of polymerisation stages, but any number is possible.
- any suitable reactor type known in the art may be used.
- a continuous stirred tank reactor and a loop reactor are suitable examples of useful reactor types.
- a loop reactor is preferred because of its flexibility.
- the slurry polymerisation may be conducted in normal liquid slurry conditions or alternatively so that the temperature and the pressure within the reactor exceed the critical temperature and pressure of the fluid mixture within the reactor.
- Such a polymerisation method is called supercritical slurry polymerisation.
- Description of liquid slurry polymerisation is given, among others, in EP 249689 and US 3262922 and supercritical slurry polymerisation in WO 92/12181 and US 3294772.
- the slurry may be withdrawn from the reactor in any method known in the art, including continuous and intermittent withdrawal. If the withdrawal is intermittent, it maybe realised by using so called settling legs, where the slurry is allowed to settle before discharging the settled slurry from the reactor. Settling legs are generally known in the art and they are described, for instance, in US 4613484 and US 4121029.
- the slurry is withdrawn continuously from the reactor, then it may be withdrawn without a concentration step or it may be concentrated either before or after the withdrawal. For economical reasons it is preferred to concentrate the slurry. Suitable methods of concentration are, among others, hydrocyclone or sieve. Typically in such a method the slurry is withdrawn continuously from the reactor and passed through a concentration device, such as hydrocyclone or sieve. The bottom flow is directed to product withdrawal whereas the overflow is recycled to the polymerisation reactor. Such methods are disclosed in EP 1415999.
- One advantage of the method of the invention is that if combined with a continuous product withdrawal, it allows a truly continuous operation of the process. As both the catalyst feed and the product withdrawal are continuous, the polymerisation process is less likely to be disturbed by catalyst feed batches or product outtake batches. The process can be operated in a more stable fashion and this leads to problem-free and stable production.
- the present invention has also advantages over similar types of arrangements, where the catalyst is mixed with oil and a viscous wax.
- the present system is simpler, as it only contains one component to mix the catalyst with.
- the present invention surprisingly produces more stable catalyst feed than the oil-wax mixture. Further still, it has been surprisingly been found that the activity of the catalyst is higher when using the feed arrangement according to the present invention. While the reason for the increased activity is not completely clear, it is believed that the highly viscous wax plugs the pores of the catalyst, thus creating a diffusion barrier.
- a further advantage of the present invention over using a mixture of oil and wax is the improved safety in catalyst handling operations.
- the catalyst slurry can be produced at a lower temperature than the wax mixture. Also, there are less treatment steps and the process is thus simpler.
- Density of the oil was measured according to ISO 12185.
- Dynamic viscosity of the oil was obtained as the product of the kinematic viscosity and the density.
- Average molecular weights and molecular weight distribution were determined by size exclusion chromatography (SEC) using Waters Alliance GPCV2000 instrument with online viscometer. Oven temperature was 140 °C. Trichlorobenzene was used as a solvent.
- Melt flow rate of the polymer was determined according to ISO 1133 at 190 0 C under a load of 2.16 kg (MFR 2 ).
- Density of the polymer was determined according to ISO 1183-1987.
- a catalyst supplied by Engelhard under the trade name Lynx 200TM was used as a polymerisation catalyst. 30.1 kg of this catalyst was suspended in 102.9 kg of Drakeol 35 oil, supplied by Penreco, to produce a catalyst slurry containing 22.6 % by weight solids. The temperature of the slurry was maintained at about 40 °C.
- the catalyst was metered into a prepolymerisation reactor having a volume of 11 m 3 by Orlita DR 15/12 non valve piston pump, where ethylene was homopolymerised in propane diluent at 60 bar pressure and at the temperature of 40 °C. The kinematic viscosity of the oil was 66 cSt and the density 865 kg/m 3 .
- the dynamic viscosity was thus 57 mPa-s.
- the feed rate of the catalyst slurry was such that approximately 0.3 kg/h of solid catalyst component was introduced into the prepolymerisation reactor.
- about 5 kg/h of a solution of 10 % by weight of triethylaluminium in pentane was introduced into the reactor.
- Ethylene, propane diluent and hydrogen were fed into the reactor in such amounts that the ethylene concentration was 1.6 % by mole and the hydrogen to ethylene ratio was 50 mol/ 100 mol.
- the resulting polymer had a melt flow index MFR 2 of 20 g/10 min and density of 960 kg/m 3 .
- the production rate was 0.36 tons/h.
- the polymer slurry was continuously withdrawn from the prepolymerisation reactor and introduced into a loop reactor where additional propane diluent, ethylene and hydrogen were introduced so that the ethylene concentration was about 7 % by mole and the molar ratio of hydrogen to ethylene was about 700 mol/kmol.
- the temperature in the loop reactor was 95 0 C and the pressure 59 bar.
- the polymer production rate in the loop reactor was about 7.5 tons/h and the polymer had a melt index MFR 2 of about 300 g/10 min and a density of about 975 kg/m 3 .
- the polymer slurry was continuously withdrawn from the loop reactor, after which the hydrocarbons were removed and the polymer was transferred to a gas phase reactor for subsequent polymerisation by adding ethylene, hydrogen and 1- butene comonomer.
- Example 2 The procedure was the same as in Example 1 but the catalyst slurry contained 7 % by weight heptane.
- the catalyst amount was 30.0 kg, oil 93.7 kg and heptane 9.3 kg.
- Catalyst solid concentration was 22.5 % by weight.
- the dynamic viscosity of the oil/heptane solution was about 15 mPa-s.
- Example 2 The procedure was the same as in Example 1 but the catalyst slurry was fed in gel thickened mineral oil i.e. wax. The catalyst amount was 20.0 kg and wax 113.3 kg. The suspension contained: Catalyst 14.8 wt-%, Drakeol 21.3 wt-% Petrolatum (wax) 63.9 wt- %. The dynamic viscosity of the mixture was 3500 m Pas.
- Catalyst feed was not that stable as in Example 1.
- One third of the catalyst mixture didn't come out from the Catalyst Mix Tank.
- a thick layer of the catalyst wax mixture remained on the wall of the Catalyst Mix Tank.
- a catalyst supplied by Engelhard under the trade name Lynx 200TM was used as a polymerisation catalyst.
- the catalyst feed arrangement was as described in EP 428056.
- the feeder works with shot injector principle and catalyst has to settle into the feed valve before each shot.
- Catalyst feed was unstable and there were big fluctuations in the prepolymerisation reactor and in the loop reactor. The process could be operated only for some hours before it had to be shut down due to a blockage in the catalyst feed and in the prepolymerisation reactor.
- Example 6 The procedure was the same as in Example 5 except that a catalyst component prepared according to EP 491566 was used as the solid catalyst component. Again the feed pump worked well without any problems.
- Example 7 The procedure was the same as in example 5 except that a silica supported metallocene catalyst prepared according to Example 2 of WO 95/12622 was used as the solid catalyst component. The feed pump worked well without problems.
- Example 8 A portion of the catalyst slurry prepared according to Example 1 was placed into a closed measurement cell made of glass and having a volume of about 200 ml and a diameter of 35 mm, where the settling velocity was measured as follows. About 100 ml of the suspension was taken into the cell and mixed by shaking, after which it was allowed to stand. The level of the catalyst free zone at the surface of the suspension was monitored visually as a function of time. It was found that the depth of the catalyst free zone increased by 10 mm/h. After 100 hours the catalyst had formed sediment at the bottom, which could only be broken by vigorous shaking.
- Example 9 A slurry prepared according to Example 1 was prepared, except a drag reducing agent NECADD 447TM, supplied by M-I Production Chemicals, was added to the composition, corresponding to an amount of 25 parts per million (ppm) in oil. The measurement was conducted as described in Example 8. No catalyst free zone could be observed at the surface of the suspension and no sediment was formed at the bottom.
- NECADD 447TM supplied by M-I Production Chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2005315889A AU2005315889A1 (en) | 2004-12-17 | 2005-12-12 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
CN2005800401330A CN101065181B (en) | 2004-12-17 | 2005-12-12 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
BRPI0519065A BRPI0519065B1 (en) | 2004-12-17 | 2005-12-12 | process for producing olefin polymers, composition and use thereof for transport and storage of solid catalyst components |
US11/667,635 US7645843B2 (en) | 2004-12-17 | 2005-12-12 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
EA200701059A EA012017B1 (en) | 2004-12-17 | 2005-12-12 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04078426A EP1671697B1 (en) | 2004-12-17 | 2004-12-17 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
EP04078426.6 | 2004-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006063771A1 true WO2006063771A1 (en) | 2006-06-22 |
Family
ID=34928749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/013315 WO2006063771A1 (en) | 2004-12-17 | 2005-12-12 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
Country Status (11)
Country | Link |
---|---|
US (1) | US7645843B2 (en) |
EP (1) | EP1671697B1 (en) |
CN (1) | CN101065181B (en) |
AT (1) | ATE401123T1 (en) |
AU (1) | AU2005315889A1 (en) |
BR (1) | BRPI0519065B1 (en) |
DE (1) | DE602004015128D1 (en) |
EA (1) | EA012017B1 (en) |
ES (1) | ES2309445T3 (en) |
WO (1) | WO2006063771A1 (en) |
ZA (1) | ZA200704270B (en) |
Cited By (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2072589A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Process for coating a pipe with high throughput using multimodal ethylene copolymer, and coated pipes obtained thereof |
EP2072586A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Coated pipes having improved mechanical properties and a method of production thereof |
EP2072587A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Coated pipes having improved mechanical properties at elevated temperatures and a method of production thereof |
EP2072588A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Process for coating a pipe with high throughput using multimodal ethylene copolymer, and coated pipes obtained thereof |
EP2186833A1 (en) | 2008-11-17 | 2010-05-19 | Borealis AG | Multi-stage process for producing polytheylene with lowered gel formation |
EP2223943A1 (en) | 2009-02-25 | 2010-09-01 | Borealis AG | Multimodal polymer of propylene, composition containing the same and a process for manufacturing the same |
EP2402376A1 (en) | 2010-06-29 | 2012-01-04 | Borealis AG | Process for producing a prepolymerised catalyst, such prepolymerised catalyst and its use for producing a polymer |
EP2570455A1 (en) | 2011-09-16 | 2013-03-20 | Borealis AG | Polyethylene composition with broad molecular weight distribution and improved homogeneity |
EP2599828A1 (en) | 2011-12-01 | 2013-06-05 | Borealis AG | Multimodal polyethylene composition for the production of pipes with improved slow crack growth resistance |
EP2711073A1 (en) | 2012-09-24 | 2014-03-26 | Borealis AG | Storage and transportation of a catalyst for a production of olefin polymers |
EP2740761A1 (en) | 2012-12-05 | 2014-06-11 | Borealis AG | Polyethylene composition with improved balance of slow crack growth resistance, impact performance and pipe pressure resistance for pipe applications |
EP2860202A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | High temperature resistant polyethylene and process for the production thereof |
EP2860201A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | High temperature resistant polyethylene and process for the production thereof |
EP2860200A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | Polyethylene composition for pipe and pipe coating applications |
EP2860204A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | Polyethylene composition for pipe applications |
EP2894174A1 (en) | 2013-12-20 | 2015-07-15 | Borealis AG | Polyethylene composition with high flexibility and high temperature resistance suitable for pipe applications |
WO2016097193A1 (en) | 2014-12-18 | 2016-06-23 | Borealis Ag | Ziegler-natta catalyst and preparation thereof |
EP3037436A1 (en) | 2014-12-22 | 2016-06-29 | Borealis AG | Process for producing multimodal polyethylene in-situ blends including ultra-high molecular weight fractions |
EP3037471A1 (en) | 2014-12-22 | 2016-06-29 | Borealis AG | Process for producing multimodal polyethylene compositions |
WO2018060029A1 (en) | 2016-09-28 | 2018-04-05 | Borealis Ag | Process for producing a coated pipe |
WO2018095790A1 (en) | 2016-11-25 | 2018-05-31 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
EP3339333A1 (en) | 2016-12-22 | 2018-06-27 | Borealis AG | Ziegler-natta catalyst and preparation thereof |
WO2019081529A1 (en) | 2017-10-24 | 2019-05-02 | Borealis Ag | Catalysts |
WO2019129650A1 (en) | 2017-12-28 | 2019-07-04 | Borealis Ag | Catalyst and preparation thereof |
WO2019129797A1 (en) | 2017-12-27 | 2019-07-04 | Borealis Ag | Ziegler-natta catalyst and preparation thereof |
US10364310B2 (en) | 2015-02-05 | 2019-07-30 | Borealis Ag | Process for producing polyethylene |
EP3567061A1 (en) | 2018-05-09 | 2019-11-13 | Borealis AG | Polypropylene pipe composition |
WO2020016370A1 (en) | 2018-07-19 | 2020-01-23 | Borealis Ag | Process for the preparation of an uhmwpe homopolymer |
EP3647645A1 (en) | 2018-10-31 | 2020-05-06 | Borealis AG | Polyethylene composition for high pressure resistant pipes |
WO2020088987A1 (en) | 2018-10-31 | 2020-05-07 | Borealis Ag | Polyethylene composition for high pressure resistant pipes with improved homogeneity |
WO2020127859A1 (en) | 2018-12-21 | 2020-06-25 | Borealis Ag | Catalyst and preparation thereof |
WO2020136164A1 (en) | 2018-12-28 | 2020-07-02 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
WO2020136165A1 (en) | 2018-12-28 | 2020-07-02 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
WO2021064078A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
WO2021064080A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
WO2021064081A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
WO2021064083A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
EP3875503A1 (en) | 2020-03-02 | 2021-09-08 | Borealis AG | Catalyst and preparation thereof |
EP3892653A1 (en) | 2020-04-09 | 2021-10-13 | Borealis AG | (co)polymerization of ethylene |
WO2022008608A1 (en) | 2020-07-10 | 2022-01-13 | Borealis Ag | Polyolefin composition with improved resistance to high temperature |
WO2022008607A1 (en) | 2020-07-10 | 2022-01-13 | Borealis Ag | Polyethylene pipe resin with high resistance to slow crack growth |
EP3988587A1 (en) | 2020-10-26 | 2022-04-27 | Borealis AG | Polyolefin pipe resin with very good sagging and slow crack growth resistance |
WO2022258804A1 (en) | 2021-06-11 | 2022-12-15 | Borealis Ag | A process for producing a multimodal ethylene polymer and films prepared therefrom |
EP4201969A1 (en) | 2021-12-23 | 2023-06-28 | Borealis AG | Polyethylene composition for pipes having very good impact properties and slow crack growth resistance |
WO2023117558A1 (en) | 2021-12-23 | 2023-06-29 | Borealis Ag | Polymer composition for pipes having very good impact properties and slow crack growth resistance |
EP4209546A1 (en) | 2022-01-10 | 2023-07-12 | Abu Dhabi Polymers Co. Ltd (Borouge) LLC | Polyethylene pipe resin with improved long term hydrostatic strength |
EP4234627A1 (en) | 2022-02-25 | 2023-08-30 | Borealis AG | A polyethylene composition with improved stiffness and toughness |
EP4234614A1 (en) | 2022-02-25 | 2023-08-30 | Borealis AG | A film comprising a polyethylene composition having improved gloss |
EP4234626A1 (en) | 2022-02-25 | 2023-08-30 | Borealis AG | A polyethylene composition with improved stiffness and toughness |
EP4257640A1 (en) | 2022-04-04 | 2023-10-11 | Borealis AG | Pipe comprising a polypropylene composition |
EP4344869A1 (en) | 2022-09-30 | 2024-04-03 | Borealis AG | Multimodal ethylene copolymer composition and films comprising the same |
WO2024083689A1 (en) | 2022-10-18 | 2024-04-25 | Borealis Ag | Multilayer film |
EP4403598A1 (en) | 2023-01-23 | 2024-07-24 | Borealis AG | Polymer composition comprising recycled low density polyethylene for packaging applications |
WO2024170344A1 (en) | 2023-02-14 | 2024-08-22 | Borealis Ag | Polyethylene blend for a film layer |
US12104001B2 (en) | 2017-12-28 | 2024-10-01 | Borealis Ag | Catalyst and preparation thereof |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7615596B2 (en) | 2005-09-30 | 2009-11-10 | Chevron Phillips Chemical Company Lp | Multiple component feed methods and systems |
CN101506247B (en) * | 2006-08-25 | 2011-04-13 | 巴塞尔聚烯烃意大利有限责任公司 | Preparation of a catalytic paste for the olefin polymerization |
US8206654B2 (en) | 2008-01-07 | 2012-06-26 | Univation Technologies, Llc | Catalyst feed systems and methods for using the same |
WO2009121374A1 (en) * | 2008-03-31 | 2009-10-08 | Dsm Ip Assets B.V. | Suspension of catalyst components |
US20120227822A1 (en) * | 2009-09-16 | 2012-09-13 | Leonard James Humphreys | Assembly for reducing slurry pressure in a slurry processing system |
CN102898554B (en) * | 2011-07-27 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method, product and application of particulate poly-alpha-olefin |
CA2749835C (en) | 2011-08-23 | 2018-08-21 | Nova Chemicals Corporation | Feeding highly active phosphinimine catalysts to a gas phase reactor |
EP2617741B1 (en) | 2012-01-18 | 2016-01-13 | Borealis AG | Process for polymerizing olefin polymers in the presence of a catalyst system and a method of controlling the process |
CN108383935A (en) * | 2012-07-13 | 2018-08-10 | 尤尼威蒂恩技术有限责任公司 | The polymer melt flow ratio for the raising that the supported catalyst being saturated by the liquid reagent of supply selection obtains |
WO2014035763A1 (en) * | 2012-08-31 | 2014-03-06 | Univation Technologies, Llc | Polymerization processes using reactor components suspended in hydrocarbon gels |
EP3088458B2 (en) * | 2015-04-27 | 2022-10-05 | Abu Dhabi Polymers Company Limited (Borouge) L.L.C. | Polyethylene composition suitable for pipe applications |
EP3241611B1 (en) | 2016-05-02 | 2020-03-04 | Borealis AG | A process for feeding a polymerisation catalyst |
CN116507404A (en) | 2020-11-27 | 2023-07-28 | 北欧化工股份公司 | Catalyst feed system |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4433123A (en) * | 1979-01-29 | 1984-02-21 | Conoco Inc. | Polymerization process for drag reducing substances |
WO2001005845A1 (en) * | 1999-07-14 | 2001-01-25 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the preparation of polyethylene |
US20030175185A1 (en) * | 2000-08-16 | 2003-09-18 | Jouni Kivela | Catalyst feeding system |
WO2004054700A1 (en) * | 2002-12-13 | 2004-07-01 | Solvay Polyolefins Europe - Belgium (S.A.) | Particulate flow control process |
US20040162400A1 (en) * | 2001-01-16 | 2004-08-19 | Eaton Gerald B. | Methods for forming amorphous ultra-high molecular weight polyolefins for use as drag reducing agents |
Family Cites Families (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE248634C (en) | 1911-02-02 | 1912-06-26 | Nack S Nachf E | VALVE-LESS SUCTION AND PRESSURE PUMP |
US3262922A (en) * | 1963-02-08 | 1966-07-26 | Phillips Petroleum Co | Polymerization process |
US3294772A (en) * | 1963-06-17 | 1966-12-27 | Phillips Petroleum Co | Supercritical polymerization |
JPS6025444B2 (en) | 1976-04-13 | 1985-06-18 | 三井東圧化学株式会社 | Manufacturing method of low density polyethylene |
US4121029A (en) * | 1976-12-06 | 1978-10-17 | Phillips Petroleum Company | Polyolefin reactor system |
JPS5610506A (en) | 1979-07-09 | 1981-02-03 | Mitsui Petrochem Ind Ltd | Production of ethylene polymer composition |
DE3274720D1 (en) | 1981-07-28 | 1987-01-29 | Statiflo Inc | Static mixers |
DE3366573D1 (en) | 1982-06-24 | 1986-11-06 | Bp Chimie Sa | Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed |
US4675368A (en) * | 1982-10-04 | 1987-06-23 | Solvay & Cie. | Process for inhibiting crust formation in reactors during alpha-olefin prepolymerization modification of Ziegler catalyst |
US4613484A (en) * | 1984-11-30 | 1986-09-23 | Phillips Petroleum Company | Loop reactor settling leg system for separation of solid polymers and liquid diluent |
CN1013220B (en) * | 1985-05-02 | 1991-07-17 | 康诺科有限公司 | Improved use of flow improvers |
US4758089A (en) * | 1985-08-22 | 1988-07-19 | Tokyo Kogaku Kikai Kabushiki Kaisha | Holographic interferometer |
CH670156A5 (en) | 1986-06-17 | 1989-05-12 | Landis & Gyr Gmbh | |
FI83844C (en) | 1989-11-14 | 1991-09-10 | Neste Oy | Method and apparatus for feeding a catalytic slurry, in particular diluted catalytic slurry, to a polymerization reactor |
FI91767C (en) | 1990-04-12 | 1994-08-10 | Neste Oy | Procatalyst composition for the polymerization of olefins, its preparation and use |
FI83932C (en) | 1990-05-17 | 1991-09-25 | Neste Oy | FOERFARANDE FOER MATNING AV EN SLAMAKTIG KATALYSATOR I EN POLYMERISATIONSREAKTOR. |
DE59104667D1 (en) | 1990-08-23 | 1995-03-30 | Sulzer Chemtech Ag | Static laminar mixing device, mixing device, and use of mixing device and mixing device. |
FI86866C (en) | 1990-12-19 | 1992-10-26 | Neste Oy | FOERFARANDE FOER MODIFIERING AV CATALYSTATOR AVSEDDA FOER POLYMERISATION AV OLEFINER |
FI89929C (en) | 1990-12-28 | 1993-12-10 | Neste Oy | Process for homo- or copolymerization of ethylene |
FI86867C (en) | 1990-12-28 | 1992-10-26 | Neste Oy | FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN |
FI94164C (en) | 1991-03-21 | 1995-07-25 | Borealis Polymers Oy | Process for dosing a polymerization catalyst made liquid to a polymerization reactor |
FI88047C (en) | 1991-05-09 | 1993-03-25 | Neste Oy | Catalyst-based catalyst for polymerization of olivines |
IT1246614B (en) | 1991-06-03 | 1994-11-24 | Himont Inc | PROCEDURE FOR THE GAS PHASE POLYMERIZATION OF OLEFINS |
FI90985C (en) | 1991-10-02 | 1994-04-25 | Neste Oy | A polymerization catalyst procatalyst composition containing an efficient electron donor |
FI89500C (en) | 1991-12-31 | 1993-10-11 | Neste Oy | Procatalytic composition for homo- and copolymerization of alpha-olefins, its preparation and use |
IT1254279B (en) | 1992-03-13 | 1995-09-14 | Montecatini Tecnologie Srl | PROCEDURE FOR THE GAS PHASE POLYMERIZATION OF OLEFINS |
FI92405C (en) | 1992-12-22 | 1994-11-10 | Borealis Holding As | New olefin polymerization catalyst, process for its preparation and its use for polymerization of olefins |
FI95387C (en) * | 1992-12-29 | 1996-01-25 | Borealis As | Process for polymerizing olefins and prepolymerized catalyst composition and process for its preparation |
FI96866C (en) | 1993-11-05 | 1996-09-10 | Borealis As | Support olefin polymerization catalyst, its preparation and use |
FI942949A0 (en) | 1994-06-20 | 1994-06-20 | Borealis Polymers Oy | Prokatalysator Foer production av etenpolymerer och foerfarande Foer framstaellning daerav |
US5589539A (en) | 1994-11-23 | 1996-12-31 | Union Carbide Chemicals & Plastics Technology Corporation | Process for preparing an in situ polyethylene blend |
FI96216C (en) | 1994-12-16 | 1996-05-27 | Borealis Polymers Oy | Process for the production of polyethylene |
FI104975B (en) | 1995-04-12 | 2000-05-15 | Borealis As | Process for producing catalytic components |
FI952175A (en) | 1995-05-05 | 1996-11-06 | Borealis As | Process and catalyst component for homo- and copolymerization of the olefin |
NO300220B1 (en) | 1996-01-26 | 1997-04-28 | Borealis As | Process and catalyst system for the polymerization of ethylene, optionally with <alfa> olefins, and polymeric material prepared |
US5869570A (en) * | 1996-03-19 | 1999-02-09 | Energy & Environmental International, L.C. | Composition of and process for forming polyalphaolefin drag reducing agents |
FI102070B (en) | 1996-03-29 | 1998-10-15 | Borealis As | A new complex compound, its preparation and use |
DE59605822D1 (en) | 1996-07-05 | 2000-10-05 | Sulzer Chemtech Ag Winterthur | Static mixer |
FI972230A (en) | 1997-01-28 | 1998-07-29 | Borealis As | New homogeneous catalyst composition for polymerization of olefins |
JP2002504954A (en) | 1997-06-24 | 2002-02-12 | ボレアリス エイ/エス | Method for producing propylene polymer |
FI111848B (en) | 1997-06-24 | 2003-09-30 | Borealis Tech Oy | Process and equipment for the preparation of homopolymers and copolymers of propylene |
FI111372B (en) | 1998-04-06 | 2003-07-15 | Borealis Polymers Oy | Catalyst component for polymerization of olefins, its preparation and use thereof |
FI981034A (en) | 1998-05-08 | 1999-11-09 | Borealis Polymers Oy | HD polyethylene compositions and process for their preparation |
NO981631L (en) | 1998-04-08 | 1999-10-11 | Borealis As | Catalyst for the polymerization of ethylene, and process for its preparation |
GB9822123D0 (en) | 1998-10-09 | 1998-12-02 | Borealis As | Catalyst |
FI990283A (en) * | 1999-02-12 | 2000-08-13 | Borealis As | Catalyst system for polymerization of alpha olefins and its use for polymerization of alpha olefins |
GB0001914D0 (en) | 2000-01-27 | 2000-03-22 | Borealis Polymers Oy | Catalyst |
EP1125626B1 (en) | 2000-02-17 | 2005-11-02 | Sulzer Chemtech AG | Static mixer |
EP1270610B8 (en) | 2001-06-20 | 2006-09-27 | Borealis Technology Oy | Preparation of olefin polymerisation catalyst component |
DE60120389T2 (en) | 2001-06-20 | 2007-06-14 | Borealis Technology Oy | Preparation of a catalyst component for olefin polymerization |
GB0126147D0 (en) | 2001-10-31 | 2002-01-02 | Borealis Tech Oy | Process |
EP1323747A1 (en) | 2001-12-19 | 2003-07-02 | Borealis Technology Oy | Production of olefin polymerisation catalysts |
JP2004094617A (en) * | 2002-08-30 | 2004-03-25 | Fujitsu Ltd | Backup method by difference compression, system and difference compression method |
DE60223926T2 (en) | 2002-10-30 | 2008-11-13 | Borealis Technology Oy | Process and apparatus for the production of olefin polymers |
US7313434B2 (en) | 2002-11-25 | 2007-12-25 | Regents Of The University Of Minnesota | Impedance monitoring for detecting pulmonary edema and thoracic congestion |
CN1221577C (en) * | 2003-03-11 | 2005-10-05 | 中国石油天然气股份有限公司 | Preparation method of poly alpha-olefin drag reducer for pipeline oil product |
-
2004
- 2004-12-17 ES ES04078426T patent/ES2309445T3/en active Active
- 2004-12-17 DE DE602004015128T patent/DE602004015128D1/en active Active
- 2004-12-17 EP EP04078426A patent/EP1671697B1/en active Active
- 2004-12-17 AT AT04078426T patent/ATE401123T1/en not_active IP Right Cessation
-
2005
- 2005-12-12 BR BRPI0519065A patent/BRPI0519065B1/en active IP Right Grant
- 2005-12-12 AU AU2005315889A patent/AU2005315889A1/en not_active Abandoned
- 2005-12-12 EA EA200701059A patent/EA012017B1/en not_active IP Right Cessation
- 2005-12-12 WO PCT/EP2005/013315 patent/WO2006063771A1/en not_active Application Discontinuation
- 2005-12-12 US US11/667,635 patent/US7645843B2/en active Active
- 2005-12-12 CN CN2005800401330A patent/CN101065181B/en active Active
-
2007
- 2007-05-24 ZA ZA200704270A patent/ZA200704270B/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4433123A (en) * | 1979-01-29 | 1984-02-21 | Conoco Inc. | Polymerization process for drag reducing substances |
WO2001005845A1 (en) * | 1999-07-14 | 2001-01-25 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the preparation of polyethylene |
US20030175185A1 (en) * | 2000-08-16 | 2003-09-18 | Jouni Kivela | Catalyst feeding system |
US20040162400A1 (en) * | 2001-01-16 | 2004-08-19 | Eaton Gerald B. | Methods for forming amorphous ultra-high molecular weight polyolefins for use as drag reducing agents |
WO2004054700A1 (en) * | 2002-12-13 | 2004-07-01 | Solvay Polyolefins Europe - Belgium (S.A.) | Particulate flow control process |
Cited By (90)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2072589A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Process for coating a pipe with high throughput using multimodal ethylene copolymer, and coated pipes obtained thereof |
EP2072586A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Coated pipes having improved mechanical properties and a method of production thereof |
EP2072587A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Coated pipes having improved mechanical properties at elevated temperatures and a method of production thereof |
EP2072588A1 (en) | 2007-12-20 | 2009-06-24 | Borealis Technology Oy | Process for coating a pipe with high throughput using multimodal ethylene copolymer, and coated pipes obtained thereof |
US8361578B2 (en) | 2007-12-20 | 2013-01-29 | Borealis Technology Oy | Process for coating a pipe with high throughput using multimodal ethylene copolymer, and coated pipes obtained thereof |
US8623482B2 (en) | 2007-12-20 | 2014-01-07 | Borealis Technology Oy | Coated pipe with high throughput using multimodal ethylene copolymer |
EP2186833A1 (en) | 2008-11-17 | 2010-05-19 | Borealis AG | Multi-stage process for producing polytheylene with lowered gel formation |
EP2223943A1 (en) | 2009-02-25 | 2010-09-01 | Borealis AG | Multimodal polymer of propylene, composition containing the same and a process for manufacturing the same |
WO2010097409A1 (en) | 2009-02-25 | 2010-09-02 | Borealis Ag | Multimodal polymer of propylene, composition containing the same and a process for manufacturing the same |
EP2402376A1 (en) | 2010-06-29 | 2012-01-04 | Borealis AG | Process for producing a prepolymerised catalyst, such prepolymerised catalyst and its use for producing a polymer |
WO2012000956A1 (en) | 2010-06-29 | 2012-01-05 | Borealis Ag | Process for producing a prepolymerised catalyst, such prepolymerised catalyst and its use for producing a polymer |
EP2570455A1 (en) | 2011-09-16 | 2013-03-20 | Borealis AG | Polyethylene composition with broad molecular weight distribution and improved homogeneity |
WO2013037498A1 (en) | 2011-09-16 | 2013-03-21 | Borealis Ag | Polyethylene composition with broad molecular weight distribution and improved homogeneity |
WO2013037432A1 (en) | 2011-09-16 | 2013-03-21 | Borealis Ag | Polyethylene composition with broad molecular weight distribution and improved homogeneity |
EP2599828A1 (en) | 2011-12-01 | 2013-06-05 | Borealis AG | Multimodal polyethylene composition for the production of pipes with improved slow crack growth resistance |
WO2013079180A1 (en) | 2011-12-01 | 2013-06-06 | Borealis Ag | Multimodal polyethylene composition for the production of pipes with improved slow crack growth resistance |
EP2711073A1 (en) | 2012-09-24 | 2014-03-26 | Borealis AG | Storage and transportation of a catalyst for a production of olefin polymers |
WO2014044859A1 (en) | 2012-09-24 | 2014-03-27 | Borealis Ag | Storage and transportation of a catalyst for a production of olefin polymers |
EP2740761A1 (en) | 2012-12-05 | 2014-06-11 | Borealis AG | Polyethylene composition with improved balance of slow crack growth resistance, impact performance and pipe pressure resistance for pipe applications |
US9527934B2 (en) | 2013-10-10 | 2016-12-27 | Borealis Ag | Polyethylene composition for pipe and pipe coating applications |
EP2860201A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | High temperature resistant polyethylene and process for the production thereof |
EP2860200A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | Polyethylene composition for pipe and pipe coating applications |
EP2860204A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | Polyethylene composition for pipe applications |
WO2015051882A1 (en) | 2013-10-10 | 2015-04-16 | Borealis Ag | High temperature resistant polyethylene and process for the production thereof |
WO2015051880A1 (en) | 2013-10-10 | 2015-04-16 | Borealis Ag | High temperature resistant polyethylene and process for the production thereof |
WO2015051879A1 (en) | 2013-10-10 | 2015-04-16 | Borealis Ag | Polyethylene composition for pipe applications |
EP2860202A1 (en) | 2013-10-10 | 2015-04-15 | Borealis AG | High temperature resistant polyethylene and process for the production thereof |
US10202504B2 (en) | 2013-12-20 | 2019-02-12 | Borealis Ag | Polyethylene composition with high flexibility and high temperature resistance suitable for pipe applications |
EP2894174A1 (en) | 2013-12-20 | 2015-07-15 | Borealis AG | Polyethylene composition with high flexibility and high temperature resistance suitable for pipe applications |
WO2016097193A1 (en) | 2014-12-18 | 2016-06-23 | Borealis Ag | Ziegler-natta catalyst and preparation thereof |
EP3037436A1 (en) | 2014-12-22 | 2016-06-29 | Borealis AG | Process for producing multimodal polyethylene in-situ blends including ultra-high molecular weight fractions |
EP3037471A1 (en) | 2014-12-22 | 2016-06-29 | Borealis AG | Process for producing multimodal polyethylene compositions |
US10669410B2 (en) | 2014-12-22 | 2020-06-02 | Borealis Ag | Process for producing multimodal polyethylene in-situ blends including ultra-high molecular weight fractions |
US10364310B2 (en) | 2015-02-05 | 2019-07-30 | Borealis Ag | Process for producing polyethylene |
US10800864B2 (en) | 2015-02-05 | 2020-10-13 | Borealis Ag | Process for producing polyethylene |
WO2018060029A1 (en) | 2016-09-28 | 2018-04-05 | Borealis Ag | Process for producing a coated pipe |
US10899942B2 (en) | 2016-09-28 | 2021-01-26 | Borealis Ag | Process for producing a coated pipe |
WO2018095788A1 (en) | 2016-11-25 | 2018-05-31 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
US11180586B2 (en) | 2016-11-25 | 2021-11-23 | Borealis Ag | Process for producing polyolefin film composition and films prepared thereof |
US10982025B2 (en) | 2016-11-25 | 2021-04-20 | Borealis Ag | Process for producing polyolefin film composition and films prepared thereof |
WO2018095790A1 (en) | 2016-11-25 | 2018-05-31 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
WO2018114347A1 (en) | 2016-12-22 | 2018-06-28 | Borealis Ag | Ziegler-natta catalyst and preparation thereof |
EP3339333A1 (en) | 2016-12-22 | 2018-06-27 | Borealis AG | Ziegler-natta catalyst and preparation thereof |
WO2019081529A1 (en) | 2017-10-24 | 2019-05-02 | Borealis Ag | Catalysts |
US11279777B2 (en) | 2017-10-24 | 2022-03-22 | Borealis Ag | Catalysts |
WO2019129797A1 (en) | 2017-12-27 | 2019-07-04 | Borealis Ag | Ziegler-natta catalyst and preparation thereof |
US11447580B2 (en) | 2017-12-27 | 2022-09-20 | Borealis Ag | Ziegler-Natta catalyst and preparation thereof |
WO2019129650A1 (en) | 2017-12-28 | 2019-07-04 | Borealis Ag | Catalyst and preparation thereof |
US11753486B2 (en) | 2017-12-28 | 2023-09-12 | Borealis Ag | Catalyst and preparation thereof |
US12104001B2 (en) | 2017-12-28 | 2024-10-01 | Borealis Ag | Catalyst and preparation thereof |
WO2019215108A1 (en) | 2018-05-09 | 2019-11-14 | Borealis Ag | Polypropylene pipe composition |
EP3567061A1 (en) | 2018-05-09 | 2019-11-13 | Borealis AG | Polypropylene pipe composition |
US11680114B2 (en) | 2018-07-19 | 2023-06-20 | Borealis Ag | Process for the preparation of an UHMWPE homopolymer |
US11965052B2 (en) | 2018-07-19 | 2024-04-23 | Borealis Ag | Process for the preparation of an UHMWPE homopolymer |
WO2020016370A1 (en) | 2018-07-19 | 2020-01-23 | Borealis Ag | Process for the preparation of an uhmwpe homopolymer |
EP3647645A1 (en) | 2018-10-31 | 2020-05-06 | Borealis AG | Polyethylene composition for high pressure resistant pipes |
WO2020089003A1 (en) | 2018-10-31 | 2020-05-07 | Borealis Ag | Polyethylene composition for high pressure resistant pipes |
WO2020088987A1 (en) | 2018-10-31 | 2020-05-07 | Borealis Ag | Polyethylene composition for high pressure resistant pipes with improved homogeneity |
WO2020127859A1 (en) | 2018-12-21 | 2020-06-25 | Borealis Ag | Catalyst and preparation thereof |
US11827733B2 (en) | 2018-12-21 | 2023-11-28 | Borealis Ag | Catalyst and preparation thereof |
WO2020136165A1 (en) | 2018-12-28 | 2020-07-02 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
WO2020136164A1 (en) | 2018-12-28 | 2020-07-02 | Borealis Ag | A process for producing polyolefin film composition and films prepared thereof |
WO2021064081A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
WO2021064080A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
WO2021064083A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
WO2021064078A1 (en) | 2019-10-04 | 2021-04-08 | Borealis Ag | Ziegler-natta catalysts for olefin polymerization |
EP3875503A1 (en) | 2020-03-02 | 2021-09-08 | Borealis AG | Catalyst and preparation thereof |
WO2021175836A1 (en) | 2020-03-02 | 2021-09-10 | Borealis Ag | Catalyst and preparation thereof |
EP3892653A1 (en) | 2020-04-09 | 2021-10-13 | Borealis AG | (co)polymerization of ethylene |
WO2021204979A1 (en) | 2020-04-09 | 2021-10-14 | Borealis Ag | (co)polymerization of ethylene |
WO2022008607A1 (en) | 2020-07-10 | 2022-01-13 | Borealis Ag | Polyethylene pipe resin with high resistance to slow crack growth |
WO2022008608A1 (en) | 2020-07-10 | 2022-01-13 | Borealis Ag | Polyolefin composition with improved resistance to high temperature |
WO2022090163A1 (en) | 2020-10-26 | 2022-05-05 | Borealis Ag | Polyolefin pipe resin with very good sagging and slow crack growth resistance |
EP3988587A1 (en) | 2020-10-26 | 2022-04-27 | Borealis AG | Polyolefin pipe resin with very good sagging and slow crack growth resistance |
WO2022258804A1 (en) | 2021-06-11 | 2022-12-15 | Borealis Ag | A process for producing a multimodal ethylene polymer and films prepared therefrom |
WO2023117558A1 (en) | 2021-12-23 | 2023-06-29 | Borealis Ag | Polymer composition for pipes having very good impact properties and slow crack growth resistance |
EP4201969A1 (en) | 2021-12-23 | 2023-06-28 | Borealis AG | Polyethylene composition for pipes having very good impact properties and slow crack growth resistance |
EP4209546A1 (en) | 2022-01-10 | 2023-07-12 | Abu Dhabi Polymers Co. Ltd (Borouge) LLC | Polyethylene pipe resin with improved long term hydrostatic strength |
WO2023131480A1 (en) | 2022-01-10 | 2023-07-13 | Abu Dhabi Polymers Co. Ltd (Borouge) Llc | Polyethylene pipe resin with improved long term hydrostatic strength |
EP4234626A1 (en) | 2022-02-25 | 2023-08-30 | Borealis AG | A polyethylene composition with improved stiffness and toughness |
EP4234627A1 (en) | 2022-02-25 | 2023-08-30 | Borealis AG | A polyethylene composition with improved stiffness and toughness |
EP4234614A1 (en) | 2022-02-25 | 2023-08-30 | Borealis AG | A film comprising a polyethylene composition having improved gloss |
EP4257640A1 (en) | 2022-04-04 | 2023-10-11 | Borealis AG | Pipe comprising a polypropylene composition |
WO2023194276A1 (en) | 2022-04-04 | 2023-10-12 | Borealis Ag | Pipe comprising a polypropylene composition |
EP4344869A1 (en) | 2022-09-30 | 2024-04-03 | Borealis AG | Multimodal ethylene copolymer composition and films comprising the same |
WO2024068977A1 (en) | 2022-09-30 | 2024-04-04 | Borealis Ag | Multimodal ethylene copolymer composition and films comprising the same |
WO2024083689A1 (en) | 2022-10-18 | 2024-04-25 | Borealis Ag | Multilayer film |
EP4403598A1 (en) | 2023-01-23 | 2024-07-24 | Borealis AG | Polymer composition comprising recycled low density polyethylene for packaging applications |
WO2024156640A1 (en) | 2023-01-23 | 2024-08-02 | Borealis Ag | Polymer composition comprising recycled low density polyethylene for packaging applications |
WO2024170344A1 (en) | 2023-02-14 | 2024-08-22 | Borealis Ag | Polyethylene blend for a film layer |
Also Published As
Publication number | Publication date |
---|---|
CN101065181B (en) | 2010-12-01 |
CN101065181A (en) | 2007-10-31 |
AU2005315889A1 (en) | 2006-06-22 |
DE602004015128D1 (en) | 2008-08-28 |
BRPI0519065B1 (en) | 2016-11-16 |
EP1671697B1 (en) | 2008-07-16 |
EA012017B1 (en) | 2009-06-30 |
ATE401123T1 (en) | 2008-08-15 |
EP1671697A1 (en) | 2006-06-21 |
EA200701059A1 (en) | 2007-12-28 |
US20070299220A1 (en) | 2007-12-27 |
US7645843B2 (en) | 2010-01-12 |
BRPI0519065A2 (en) | 2008-12-23 |
ZA200704270B (en) | 2008-09-25 |
ES2309445T3 (en) | 2008-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7645843B2 (en) | Process for polymerising olefins in the presence of an olefin polymerisation catalyst | |
US7904271B2 (en) | Method and system for determining catalyst activity | |
CN105283470B (en) | Polymerization in the presence of antistatic property composition | |
US20140045988A1 (en) | Novel polymer composition for use in blow moulding | |
KR20120115326A (en) | Method for producing a catalyst slurry blend | |
US10946357B2 (en) | Process for feeding a polymerisation catalyst | |
EP1563902A1 (en) | Method and apparatus for preparing and supplying catalyst slurry to a polymerization reactor. | |
EP2598783B1 (en) | Method for metering a catalyst slurry | |
US20240001317A1 (en) | Catalyst Feed System | |
US20220195085A1 (en) | Rapid dissolution of drag-reducing agents at low temperatures | |
WO2021122992A1 (en) | Polymerization process and reactor for controlling molecular weight distribution and comonomer composition distribution | |
JPH08225612A (en) | Ethylene polymer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005315889 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11667635 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200580040133.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2005315889 Country of ref document: AU Date of ref document: 20051212 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023/KOLNP/2007 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200701059 Country of ref document: EA |
|
WWP | Wipo information: published in national office |
Ref document number: 11667635 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 05820477 Country of ref document: EP Kind code of ref document: A1 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 5820477 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: PI0519065 Country of ref document: BR |