CN103183752A - Method for preparing olefin polymer - Google Patents
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Abstract
The invention provides a method for preparing olefin polymer by a fluidized bed reactor; the temperature in the fluidized bed reactor is controlled to provide at least one low temperature area in the reactor; the polymerization temperature approaches or is equal to a dew point temperature of fluidizing gas in the reactor, particularly the temperature difference between the two is +/- 5 DEG C. According to the method of the invention, the fluidized bed reactor is operated; the polymer generated by copolymerization of ethene and alpha-olefin has a same melt index and density, and physical properties of the olefin polymer is characterized, such as tensile strength including yield strength and breaking tenacity, and falling dart impact, which are improved greatly.
Description
Technical field
The present invention relates to a kind of method for preparing olefin polymer, specifically is to realize by the temperature of controlling different zones in the fluidized-bed reactor.
Background technology
As everyone knows, olefin polymer widespread use in each field, the rigidity that it has, toughness, lightweight are that many materials can not replace, improving and improving the alkene performance also is the target that the scientific research personnel constantly pursues.In the process of manufacturing olefin polymer well known in the art, gas-phase fluidized-bed reactor is a kind of olefin polymerization reactor of safer, environmental protection, and it can select Z-N, metallocene or chromium-based catalysts to make the lower polymkeric substance of olefinic polymerization production density, this be non-fluidized-bed reactor can't be obtained.But, because olefinic polyreaction heat is big (being about 800kcal/kg-PE), the rate-constrained system that shifts out of the lower thereby heat of reaction of the heat transfer efficiency of gas and thermal capacity makes the easy local superheating of reactor bed and causes instability that this is the thin spot of conventional flow fluidized bed reactor technology.
Disclosed gas fluidised bed polymerisation reaction unit is formed airtight circulation loop by fluidized-bed reactor, recycle gas compressor, a recycle gas cooler among the patent US4379758,4383095 and 4876320, recycle gas cycle operation in the loop of being formed by reaction monomers ethene, alpha-olefin, hydrogen and inert nitrogen gas, keep polymkeric substance all the time fluidisation and heat of polymerization shift out, the polymerization temperature in the control whole reactor is at a certain steady state value.
For making the fluidized-bed reactor internal temperature more uniform and stable, patent US3254070,3300457,3652527 and 4012573 has announced and liquid spray gone into or has injected on the polymer bed or polymer bed in the fluidized-bed reactor, liquid flash distillation immediately in higher temperature flow oxidizing gases is gas phase, and purpose is to make any some temperature in the whole reactor reach constant a certain polymeric reaction temperature value in order to remove reaction heat to greatest extent.But its patent described polymeric reaction temperature value is the dew-point temperature that is higher than fluidizing agent far away, and also namely controlling in the reactor arbitrarily reflecting point or regional internal reaction thing and non-reactant all is gas phase state.
Describe a kind of reaction heat that shifts out rapidly in " gas phase polymerization process " that patent CN1133298A announces and improve the speed of response method, its purpose also is for the polymerization temperature in the stopping reaction device.Concrete grammar is to introduce a kind of inert hydrocarbon as cryogen in the circulation gaseous stream, the dew point of circulation gaseous stream is raise above the fluidized-bed reactor temperature in, the gaseous monomer logistics of recirculation reactor is compressed and cooled off, make it condensation and produce the partially liq logistics.The liquid stream that produces returns with gas stream and enters flash distillation immediately in the reactor, absorb and shift out polymerization reaction heat with the latent heat of vaporization, this operation is called as " condensation mode ", but the purpose of this working method is to improve space-time yield stablizing under a certain polymerization temperature, and does not allow that in the method free liquid is present in the gas in the fluidized-bed reactor.That is to say that polymerization temperature in its reactor is the dew-point temperature that is higher than gaseous stream, reflecting point or regional internal reaction thing and non-reactant all exist with gas phase state arbitrarily in the reactor.
Comprehensively above-mentioned, think for a long time in the control fluidized-bed reactor always stable phase in each zone with and the temperature of reaction that is higher than fluidizing agent dew-point temperature in the reactor to reactor steady running with guarantee that polymer quality is vital.Even in the working method of the polymerization reactor of above-mentioned " condensation mode ", the dew point (40～60 ℃) of control fluidisation gaseous stream just is higher than the temperature in (38～41 ℃) of reactor, and does not approach or reach fluidized-bed reactor temperature inside (vary in size be chosen in 75～90 ℃ according to density polymer).The polymeric reaction temperature that this patent is surprised to find any one polyreaction zone in the control reactor approaches or when equaling the dew-point temperature of fluidizing agent in the reactor, the physicals of olefin polymer is greatly improved.
Summary of the invention
The invention provides a kind of method of utilizing fluidized-bed reactor to prepare olefin polymer, it is characterized in that: the temperature in the control fluidized-bed reactor, make and have a low-temperature region at least in the reactor, its polymeric reaction temperature approaches or equals the dew-point temperature of fluidizing agent in the reactor, be specially the two temperatures value differ ± 5 ℃.Preferred two temperatures value differs ± and 3 ℃.
According to one embodiment of the present invention, in the circulation gas of reactor, add cryogen, make that the dew-point temperature rising of the interior described fluidizing agent of reactor is 60～78 ℃, more preferably 66～75 ℃.Described cryogen is for example for being selected from ethane, propane, butane, pentane and the hexane one or more, preferred pentane, hexane or its mixture.
In the present invention, preferred described low-temperature region subregion among 0～6m above the grid distributor in reactor.
In addition, in the present invention, the low-temperature region volume in the preferred reactor is 1/48～4/5 of whole reactor volume, and more preferably the low-temperature region volume is 1/6～1/2 of whole reactor volume.
The present invention can use gas fluidised bed polymerisation reaction unit well known to those skilled in the art in the prior art, it forms airtight circulation loop by fluidized-bed reactor, recycle gas compressor, a recycle gas cooler, recycle gas cycle operation in the loop of being formed by reaction monomers ethene, alpha-olefin, hydrogen and inert nitrogen gas, keep polymer particle fluidisation and shift out heat of polymerization all the time, described polymer particle is called as seed bed.Described seed bed plays mass-and heat-transfer and dispersed catalyst in olefin polymerization process.The catalyzer of selecting in the reactor can be Ziegler-Natta catalyst well known in the art, inorganic chromium catalyzer, organic chromium catalyzer, metallocene catalyst, the composite catalyst of preferred Ziegler-Natta catalyst, metallocene and Z-N; Described preferred catalyzer is to make olefinic polymerization generate polymkeric substance under a kind of promotor effect, and promotor comprises: trimethyl aluminium, triethyl aluminum, aluminium isobutyl, a chlorine diethyl etc., preferred triethyl aluminum.In the present invention, the working pressure of gas-phase fluidized-bed polymerizing reactor is at 0.5～3.0Mpa, preferred 12～2.5Mpa; Reactant olefin concentration is at 1.0～60.0% (v/v), alkane concentration 0.1～20.0% (v/v), density of hydrogen 0.00～10.0% (v/v), inert gas concentration 1.0～50.0% (v/v), described alkene comprises ethene, propylene, butylene, hexene, octene or higher-alkene etc., optimal ethylene hervene copolymer or ethylene octene copolymerization; Described alkane comprises ethane, propane, butane, pentane, hexane etc., and described rare gas element is nitrogen.
As shown in Figure 1, according to the present invention, the polymeric reaction temperature T of optional position in the olefin polymerization reactor
4Refer to bed temperature in the reactor.Detector unit is installed in fluidized-bed reactor bed inside radially 2mm, preferred 20mm, more preferably 200mm depths at least; With quick, reflect real polymerization temperature exactly.In the present invention, olefinic polymerization fluidized-bed reactor temperature in T
5For example be 40～43 ℃.
In one embodiment of the invention, catalyzer continuously is injected in the middle of the seed bed of fluidisation, reaction mass alkene, alkane, hydrogen and rare gas element successively enter the fluidized-bed reactor bottom, comprise introduce in the circulation gaseous stream enough inert hydrocarbons such as pentane as cryogen, the dew point of circulation gaseous stream is raise above the fluidized-bed reactor temperature in, reach the method that improves space-time yield, the olefin polymer of manufacturing is continuously discharged from reactor.Unreacted material comes out to reenter fluidized-bed reactor after overdraft, cooling from reactor head.
Described recycle gas is compressed to become liquid stream with cooling rear section cryogen and high alpha-olefin, and this liquid stream for example can enter the bottom of reactor by the grid distributor of fluidized-bed reactor, upwards flows along the reactor axial direction due then.Described liquid stream enters the fluidized-bed reactor bottom and form more than one dew-point temperature zone behind this inside reactor, makes described polymerization reactant polyreaction under described dew-point temperature; Or the liquid stream that the compression of described recycle gas and cooling back form separated with gas-liquid separation device obtain liquid phase, the liquid phase that described separation obtains is the 10%wt of total liquid stream, preferred 30%wt, more preferably more than 50%, (for example be forced into more than the 0.3Mpa with the equipment for liquid transportation pressurization again, more than the preferred 1.0Mpa) be input to the optional position of distributing plate of fluidized-bed reactor top, grid distributor top 0.5m for example, 1.0m or the position of 3.0m, in reactor, form more than one low-temperature region and make described polymerization reactant polyreaction under described dew-point temperature.
In one embodiment of the invention, control that the method for at least one low-temperature region is by reducing reactor temperature T in the described reactor
4Realizing, specifically can be to realize by control reactor exterior cooling discharge.
In another embodiment of the present invention, control that the method for at least one low-temperature region is to realize by introduce inert hydrocarbon (as pentane) cryogen in the circulation gaseous stream in the described reactor.Concrete as continuous or discontinuously in reactor, inject pentane with an impeller pump or reciprocation pump, pentane concentration in the recycle gas is reached more than above, the preferred 10.0%v/v of 5.0%v/v, the dew point of reactor outer circulation gas phase object stream is elevated between 66～68 ℃, produces liquid phase stream thereby surpass the fluidized-bed reactor temperature in; And this dew point of circulation gas gaseous stream approaches or reaches 68.3 ℃ of the boiling points of hexene-1, makes polymerization activity point form high density hexene-1 on every side, thereby can produce the relatively low polymkeric substance of density.The preferred butene-1 of alpha-olefin, hexene-1, octene-1, preferred liquids flow account for the 5wt% of recycle gas total amount, more preferably more than the 10wt%.The composition of these liquid streams comprises alkene and alkane, and alkene comprises: ethene, propylene, butylene, hexene, octene or higher alpha-olefin etc., optimal ethylene and hexene, ethene and octene or mixture; Alkane comprises: ethane, propane, butane, pentane, hexane etc., preferred pentane or hexane or their mixture.The grid distributor that this liquid stream is ejected into fluidized-bed reactor with 10～15m/s speed enters the bottom of reactor then, and these liquid streams are aggregated the heat vaporization and reduce the inside reactor temperature and form a dew-point temperature; Or the compressed liquid stream that forms with cooling back of described recycle gas separated with tripping device obtain liquid phase, be input to optional position above the distributing plate of fluidized-bed reactor with equipment for liquid transportation again.
According to the method for the invention operating fluidized bed reactor, ethene has under the identical melt index and density with the polymkeric substance that alpha-olefin copolymer produces, and the physical performance index of sign olefin polymer such as tensile strength (comprising surrender and breaking tenacity), the impact of becoming thin are all improved greatly.
Description of drawings
Fig. 1 is axial location point distribution schematic diagram in the fluidized-bed reactor among the present invention.
Embodiment
Term " melt index " refers to the melt flow rate (MFR) measured according to GB/T-3682-2000 condition (190 ℃, 2.16kg load), and is designated as MI usually
2.16
Measure the density of olefin polymer according to the GB/1033-1986 method.
Measure thickness according to the GB/T1040.1-2006 method, use the tensile strength of the method mensuration polymkeric substance of GB/T1040.1.
According to the test of the A method in GB/T9639.1-2008 method dart impact value.
Embodiment 1
Preparation of Catalyst: method for preparing catalyst prepares catalyzer in the present embodiment among the introducing patent application WO2008/116396A1.The first step is pressed Mg/Ti=5: 1 preparation Ziegler-Natta catalyst (ZN-1); second step was carried on mould material on the described Ziegler-Natta catalyst; the 3rd step was carried on (ZN-2) on the described rete, and the 4th step is stand-by with storing under the dry desolventizing of described composite catalyst, the nitrogen protection.
Polymer manufacture: be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, be comonomer production POF film product with hexene-1.Reactant consists of: ethene 27.19%v/v, hexene-1 concentration 5.613%v/v, hydrogen 5.784%v/v.88 ℃ of polymeric reaction temperatures.The concentration 300ppm that adds the promotor triethyl aluminum in the reactor, then start the catalyzer feeding equipment catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, starting the cryogen transferpump adds iso-pentane, control all the time or regulates in the circulation gas iso-pentane concentration at 10.20%v/v to reactor, the dew point of the outer circulation gaseous stream of reactor is elevated between 66～68 ℃, approaches or reach 68.3 ℃ of the boiling points of hexene-1.Then, progressively regulate catalyzer add intake rate between 2.0～2.2kg/hr control space-time yield make circulation gas at reactor inlet temperature between 40～43 ℃, recycle gas is compressed at this moment produces 20～26%wt that the liquids flow accounts for the recycle gas total amount with the cooling back, these liquid are sprayed by vapor phase stream and enter reactor lower part by the grid distributor that is arranged on reactor bottom, the dew point of fluidisation gaseous stream is elevated between 66～75 ℃, makes alkene polyreaction under this temperature.Need to prove that the temperature of reaction in the reactor in most of volume is 88 ℃, is 66～75 ℃ but this zone of convergency is the polymeric reaction temperature of low-temperature region, and this low-temperature region is roughly grid distributor and highly locates to grid distributor top 2m.
The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 2.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 2.It is the interior operational condition of reactor of the olefinic polyreaction in each embodiment and the Comparative Examples in the table 1.
Embodiment 2
Preparation of Catalyst is with embodiment 1.
Polymer manufacture: be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, be comonomer production POF film product with hexene-1.Reactant consists of: ethene 27.34v/v, hexene-1 concentration 4.90%v/v, hydrogen 4.67%v/v.88 ℃ of polymeric reaction temperatures.The concentration 300ppm that adds the promotor triethyl aluminum in the reactor, then start the catalyzer feeding equipment catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, starting the cryogen transferpump adds iso-pentane, control all the time or regulates in the circulation gas iso-pentane concentration at 8.50%v/v to reactor, the dew point of the outer circulation gaseous stream of reactor is elevated between 66～68 ℃, approaches or reach 68.3 ℃ of the boiling points of hexene-1.Then, progressively regulate catalyzer add intake rate between 2.0～2.2kg/hr control space-time yield make circulation gas at reactor inlet temperature between 40～43 ℃, recycle gas is compressed at this moment produces 20～26%wt that the liquids flow accounts for the recycle gas total amount with the cooling back, these liquid are separated by the pipeline separator, be pressurized to 1.2Mpa with impeller pump again and squeeze into the height place of the above 0.5m of reactor distributing plate and spray in the injecting reactor and the dew point of fluidisation gaseous stream is elevated between 66～73 ℃, make alkene polyreaction under this temperature.Wherein, 66～73 ℃ low-temperature region is roughly grid distributor and highly locates to grid distributor top 2.5m.
The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 2.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 2.
Embodiment 3
Preparation of Catalyst is with embodiment 1.
Polymer manufacture: be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, be comonomer production agricultural greenhouse film product with hexene-1.Reactant consists of: ethene 28.78%v/v, hexene-1 concentration 4.61%v/v, hydrogen 4.00%v/v.88 ℃ of polymeric reaction temperatures.The concentration 300ppm that adds the promotor triethyl aluminum in the reactor, then start the catalyzer feeding equipment catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, starting the cryogen transferpump adds iso-pentane, control all the time or regulates in the circulation gas iso-pentane concentration at 9.0%v/v to reactor, the dew point of the outer circulation gaseous stream of reactor is elevated between 66～68 ℃, approaches or reach 68.3 ℃ of the boiling points of hexene-1.Then, progressively regulate catalyzer add intake rate between 2.0～2.2kg/hr control space-time yield make circulation gas at reactor inlet temperature between 40～43 ℃, recycle gas is compressed at this moment produces 20～26%wt that the liquids flow accounts for the recycle gas total amount with the cooling back, these liquid are separated by the pipeline separator, be pressurized to 1.2Mpa with impeller pump again and squeeze into the above 1.0m of reactor distributing plate and 3.0m two highly places and spray in the injecting reactor and the dew point of fluidisation gaseous stream is elevated between 66～73 ℃, make alkene polyreaction under this temperature.Wherein, 66～73 ℃ low-temperature region is roughly grid distributor and highly locates to grid distributor top 5m.
The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 2.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 2.
Embodiment 4
Preparation of Catalyst is with embodiment 1.
Polymer manufacture: be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, be comonomer production POF film product with hexene-1.Reactant consists of: ethene 27.55v/v, hexene-1 concentration 5.38%v/v, hydrogen 5.11%v/v.88 ℃ of polymeric reaction temperatures.The concentration 300ppm that adds the promotor triethyl aluminum in the reactor, then start the catalyzer feeding equipment catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, starting the cryogen transferpump adds iso-pentane, control all the time or regulates in the circulation gas iso-pentane concentration at 10.05%v/v to reactor, the dew point of the outer circulation gaseous stream of reactor is elevated between 66～68 ℃, approaches or reach 68.3 ℃ of the boiling points of hexene-1.Then, progressively regulate catalyzer add intake rate between 2.0～2.2kg/hr control space-time yield make circulation gas at reactor inlet temperature between 40～43 ℃, recycle gas is compressed at this moment produces 20～26%wt that the liquids flow accounts for the recycle gas total amount with the cooling back, these liquid are separated by the pipeline separator, be pressurized to 1.2Mpa with impeller pump again and squeeze into the above 0.5m of reactor distributing plate, 1.0m and three of 3.0m highly in place and the injection injecting reactor, and the dew point that makes the fluidisation gaseous stream is elevated between 66～74 ℃, makes alkene polyreaction under this temperature.Wherein, 66～74 ℃ low-temperature region is roughly grid distributor and highly locates to grid distributor top 5m.
The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 2.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 2.
Comparative Examples 1
Preparation of Catalyst is with embodiment 1.
Polymer manufacture: poly-unit is identical with embodiment 1, and difference is by traditional method (temperature in the whole gas-phase fluidized-bed reactor is same temperature) operation olefine polymerization reactor of gas phase fluidized bed.Be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, produce the agricultural greenhouse film product with hexene-1 for comonomer, reactant consists of: ethene 30.78%v/v, hexene-1 concentration 4.91%v/v, hydrogen 4.30%v/v.88 ℃ of polymeric reaction temperatures add 300ppm promotor triethyl aluminum in the reactor, then start the catalyzer feeding equipment catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr.Progressively regulate catalyzer and add intake rate between 2.0～2.2kg/hr, control space-time yield make circulation gas at reactor inlet temperature at 38～41 ℃, the circulation gas dew point is at 48～50 ℃, and recycle gas is compressed at this moment produces 3～7%wt that the liquids flow accounts for the recycle gas total amount with the cooling back.The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 2.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 2.
Comparative Examples 2
Preparation of Catalyst is with embodiment 1.
Polymer manufacture: poly-unit is identical with embodiment 1, and difference is by traditional method (temperature in the whole gas-phase fluidized-bed reactor is same temperature) operation olefine polymerization reactor of gas phase fluidized bed.Be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, be comonomer production POF film product with hexene-1, reactant consists of: ethene 27.98%v/v, hexene-1 concentration 3.64%v/v, hydrogen 3.88%v/v.88 ℃ of polymeric reaction temperatures add 300ppm promotor triethyl aluminum in the reactor, then start the catalyzer feeding equipment catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr.Progressively regulate catalyzer and add intake rate between 2.0～2.2kg/hr, control space-time yield make circulation gas at reactor inlet temperature at 38～41 ℃, the circulation gas dew point is at 48～50 ℃, and recycle gas is compressed at this moment produces 3～7%wt that the liquids flow accounts for the recycle gas total amount with the cooling back.The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 2.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 2.
Table 1
Table 2
As can be seen from Table 2, among the embodiment in the melt index of polymkeric substance and density and the Comparative Examples melt index of polymkeric substance similar with density; But during by the method for the invention operating fluidized bed reactor, after the polymkeric substance that polymerization generates under the gas dew point temperature that reaction monomers is set up in reactor was made film article, physicalies such as the impact of becoming thin of film, surrender breaking tenacity had great improvement.In addition, only have the olefinic polymerization of smaller portions volume under dew-point temperature, to carry out among the embodiment 1 in the reactor, and among the embodiment 4 in the reactor three height spraying liquids of the above 0.5m of grid distributor, 1.0m and 3.0m make have the olefinic polymerization of comparatively large vol under dew-point temperature, to carry out in the reactor; Become excellent gradually from the result of embodiment 1 to embodiment 4, illustrate that the low-temperature region volume that reacts under dew-point temperature along with olefinic polymerization in the reactor is more big, the physicals of olefin polymer is improved more obvious.
Claims (10)
1. method of utilizing fluidized-bed reactor to prepare olefin polymer, it is characterized in that: the temperature in the control fluidized-bed reactor, make and have a low-temperature region at least in the reactor, its polymeric reaction temperature approaches or equals the dew-point temperature of fluidizing agent in the reactor, be specially the two temperatures value differ ± 5 ℃.
2. according to the described method of claim 1, it is characterized in that: the two temperatures value differs ± and 3 ℃.
3. according to the described method of claim 1, it is characterized in that: in circulation gas, add cryogen, make that the dew-point temperature rising of the interior described fluidizing agent of reactor is 60～78 ℃.
4. according to the described method of claim 3, it is characterized in that: the dew-point temperature of described fluidizing agent is 66～75 ℃.
5. according to the described method of claim 3, it is characterized in that: described cryogen is to be selected from ethane, propane, butane, pentane and the hexane one or more, preferred pentane, hexane or its mixture.
6. according to the described method of claim 1, it is characterized in that: described low-temperature region subregion among 0～6m above the grid distributor in reactor.
7. according to any described method in the claim 1～6, it is characterized in that: the low-temperature region volume in the reactor is 1/48～4/5 of whole reactor volume.
8. according to the described method of claim 6, it is characterized in that: the low-temperature region volume in the reactor is 1/6～1/2 of whole reactor volume.
9. according to any described method in the claim 1～6, it is characterized in that: the used catalyzer of preparation polymkeric substance is one or more in Ziegler-Natta catalyst, metallocene catalyst, Z-N and the metallocene composite catalyst, uses triethyl aluminum to be promotor.
10. according to any described method in the claim 1～6, it is characterized in that: use alkene homopolymerization or the described polymkeric substance of copolymerization, wherein alkene comprises ethene, butene-1, hexene-1, octene-1, optimal ethylene and hexene-1 or octene-1 copolymerization.
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| CN104628904A (en) * | 2015-01-28 | 2015-05-20 | 浙江大学 | Method for preparing olefin polymer by utilizing multiple temperature reaction areas |
| CN110719923A (en) * | 2017-06-20 | 2020-01-21 | 博里利斯股份公司 | Process for the polymerization of olefins, apparatus and use of the apparatus |
| CN115232239A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Ethylene-butene-octene terpolymer and preparation method and system thereof |
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| CN104558349A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Method for performing olefin polymerization by fluidized bed facility, olefin polymer prepared by method and application of olefin polymer |
| CN104628904A (en) * | 2015-01-28 | 2015-05-20 | 浙江大学 | Method for preparing olefin polymer by utilizing multiple temperature reaction areas |
| CN104628904B (en) * | 2015-01-28 | 2017-06-13 | 浙江大学 | A kind of method that utilization multi-temperature reaction zone prepares olefin polymer |
| CN110719923A (en) * | 2017-06-20 | 2020-01-21 | 博里利斯股份公司 | Process for the polymerization of olefins, apparatus and use of the apparatus |
| CN115232239A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Ethylene-butene-octene terpolymer and preparation method and system thereof |
| CN115232239B (en) * | 2021-04-22 | 2024-01-19 | 中国石油化工股份有限公司 | Ethylene-butene-octene terpolymer and preparation method and system thereof |
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