CN103183752B - Method for preparing olefin polymer - Google Patents
Method for preparing olefin polymer Download PDFInfo
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- CN103183752B CN103183752B CN201110451643.4A CN201110451643A CN103183752B CN 103183752 B CN103183752 B CN 103183752B CN 201110451643 A CN201110451643 A CN 201110451643A CN 103183752 B CN103183752 B CN 103183752B
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 42
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000004711 α-olefin Substances 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 4
- 238000013459 approach Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 52
- 239000007788 liquid Substances 0.000 description 29
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- 239000000376 reactant Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000005243 fluidization Methods 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- -1 propylene, butylene, hexene Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 preparing olefin polymer, realize particular by the temperature of different zones in control flow check fluidized bed reactor.
Background technology
As everyone knows, olefin polymer widespread use in each field, the rigidity that it has, toughness, Lightness be that many materials are not replaceable, improving Olefins is also the target that scientific research personnel constantly pursues.In the process of manufacture 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 polymkeric substance that olefinic polymerization production density is lower, this is less than non-fluidized-bed reactor.But, due to olefinic polyreaction heat comparatively large (being about 800kcal/kg-PE), the heat transfer efficiency of gas and the lower thus heat of reaction of thermal capacity shift out rate-constrained system, make the easy local superheating of reactor bed and cause instability, this is the thin spot of conventional fluidization bed bioreactor technique.
Disclosed in patent US4379758,4383095 and 4876320, gas fluidised bed polymerisation reaction unit forms airtight circulation loop by a fluidized-bed reactor, recycle gas compressor, recycle gas cooler, the recycle gas be made up of reaction monomers ethene, alpha-olefin, hydrogen and inert nitrogen gas cycle operation in the loop, keep polymkeric substance all the time fluidisation and heat of polymerization shift out, control polymerization temperature in whole reactor at a certain steady state value.
For making fluidized-bed reactor internal temperature more uniform and stable, patent US3254070,3300457,3652527 and 4012573 discloses in the polymer bed or polymer bed that to be entered by liquid spray or inject in fluidized-bed reactor, liquid flash distillation immediately in higher temperature flow oxidizing gases is gas phase, and object is a certain polymeric reaction temperature value making any point temperature in whole reactor reach constant to remove reaction heat to greatest extent.But polymeric reaction temperature value described in its patent is far away higher than the dew-point temperature of fluidizing agent, also namely to control in reactor arbitrarily in reflecting point or region reactant and non-reactant be all gas phase state.
Describe one in " gas phase polymerization process " that patent CN1133298A announces and shift out reaction heat raising speed of response method rapidly, its object is also in order to the polymerization temperature in stable reactor.Concrete grammar in circulation gaseous stream, introduces a kind of inert hydrocarbon as cryogen, the dew point of circulation gaseous stream is made to increase to over fluidized-bed reactor temperature in, the gaseous monomer logistics of recirculation reactor is compressed and cooled, is made it condensation generating portion liquid stream.The liquid stream produced returns with gas stream and enters flash distillation immediately in reactor, absorb with the latent heat of vaporization and shift out polymerization reaction heat, this operation is called as " condensation mode ", but the object of this working method improves space-time yield stablizing under a certain polymerization temperature, and do not allow in the method in the gas that free liquid is present in fluidized-bed reactor.That is polymerization temperature is the dew-point temperature higher than gaseous stream in its reactor, and in reactor, reactant and non-reactant all exist with gas phase state in reflecting point or region arbitrarily.
Comprehensively above-mentioned, to think for a long time in control flow check fluidized bed reactor always stable phase in each region with and higher than the temperature of reaction of fluidizing agent dew-point temperature in reactor to reactor steady running with ensure that polymer quality is vital.Even if in the working method of the polymerization reactor of above-mentioned " condensation mode ", control the dew point (40 ~ 60 DEG C) of fluidisation gaseous stream just higher than the temperature in (38 ~ 41 DEG C) of reactor, and there is no close to or reach the temperature (vary in size according to density polymer and select at 75 ~ 90 DEG C) of fluidized-bed reactor inside.This patent be surprised to find the polymeric reaction temperature that controls any one polyreaction region in reactor close to or equal the dew-point temperature of fluidizing agent in reactor time, the physicals of olefin polymer is greatly improved.
Summary of the invention
The invention provides a kind of fluidized-bed reactor that utilizes to prepare the method for olefin polymer, it is characterized in that: the temperature in control flow check fluidized bed reactor, make in reactor, at least to there is a low-temperature region, its polymeric reaction temperature close to or equal the dew-point temperature of fluidizing agent in reactor, be specially two temperatures value difference ± 5 DEG C.Preferred two temperatures value difference ± 3 DEG C.
According to one embodiment of the present invention, in the circulation gas of reactor, add cryogen, it is 60 ~ 78 DEG C that the dew-point temperature of described fluidizing agent in reactor is raised, and is more preferably 66 ~ 75 DEG C.One or more such as being selected from ethane, propane, butane, pentane and hexane of described cryogen, preferred pentane, hexane or its mixture.
In the present invention, the preferred subregion of described low-temperature region in reactor above grid distributor in 0 ~ 6m.
In addition, in the present invention, the low-temperature region volume in preferred reactor is 1/48 ~ 4/5 of whole reactor volume, and more preferably 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 prior art, it forms airtight circulation loop by a fluidized-bed reactor, recycle gas compressor, recycle gas cooler, the recycle gas be made up of reaction monomers ethene, alpha-olefin, hydrogen and inert nitrogen gas cycle operation in the loop, 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 selected in 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 under a kind of promotor effect, make olefinic polymerization generate polymkeric substance, 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, preferably 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 olefin polymerization reactor
4refer to bed temperature in reactor.Detector unit is arranged at least 2mm, preferably 20mm, more preferably the 200mm depths, bed inside of fluidized-bed reactor radial direction; With agility, reflect real polymerization temperature exactly.In the present invention, olefinic polymerization fluidized-bed reactor temperature in T
5be such as 40 ~ 43 DEG C.
In one embodiment of the invention, catalyzer is continuously injected in the middle of the seed bed of fluidisation, reaction mass alkene, alkane, hydrogen and rare gas element successively enter bottom fluidized-bed reactor, comprise to introduce in circulation gaseous stream enough inert hydrocarbons such as pentane as cryogen, the dew point of circulation gaseous stream is made to increase to over fluidized-bed reactor temperature in, reach the method improving space-time yield, the olefin polymer of manufacture is continuously discharged from reactor.Unreacted material out reenters fluidized-bed reactor from reactor head after overdraft, cooling.
Described recycle gas is compressed and is cooled rear section cryogen and high alpha-olefin becomes liquid stream, and this liquid stream such as can enter the bottom of reactor by the grid distributor of fluidized-bed reactor, then upwards flow along reactor axial direction due.Described liquid stream enters bottom fluidized-bed reactor and form more than one dew-point temperature region after this inside reactor, makes described polymerization reactant polyreaction under described dew-point temperature, or the liquid stream gas-liquid separation device formed after the compression of described recycle gas and cooling is separated obtains 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%, (such as more than 0.3Mpa is forced into again with equipment for liquid transportation pressurization, preferred more than 1.0Mpa) be input to optional position above distributing plate of fluidized-bed reactor, such as, above grid distributor 0.5m, the position of 1.0m or 3.0m, in reactor, form more than one low-temperature region make described polymerization reactant polyreaction under described dew-point temperature.
In one embodiment of the invention, the method controlling at least one low-temperature region in described reactor is by reducing reactor temperature T
4realizing, can be specifically realize by controlling reactor exterior cooling discharge.
In another embodiment of the present invention, the method controlling at least one low-temperature region in described reactor realizes by introducing inert hydrocarbon (as pentane) cryogen in circulation gaseous stream.Concrete as with an impeller pump or reciprocation pump continuous or discontinuously in reactor, inject pentane, the pentane concentration in recycle gas is made to reach more than 5.0%v/v, preferably more than 10.0%v/v, the dew point of reactor outer circulation gas phase object stream is elevated between 66 ~ 68 DEG C, exceedes fluidized-bed reactor temperature in thus produce liquid phase stream; And this dew point of circulation gas gaseous stream close to or reach the boiling point 68.3 DEG C of hexene-1, make to form high density hexene-1 around polymerization activity point, thus the relatively low polymkeric substance of density can be produced.The preferred butene-1 of alpha-olefin, hexene-1, octene-1, preferred liquids flow accounts for 5wt%, more preferably more than the 10wt% of recycle gas total amount.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.Then this liquid stream enters the bottom of reactor with the grid distributor that 10 ~ 15m/s speed is ejected into fluidized-bed reactor, and these liquid streams are vaporized by heat of polymerization and reduced inside reactor temperature and form a dew-point temperature; Or to be compressed by described recycle gas and be separated obtain liquid phase with the liquid stream tripping device that formed after cooling, then be input to the optional position above distributing plate of fluidized-bed reactor with equipment for liquid transportation.
According to the method for the invention operating fluidized bed reactor, the polymkeric substance that ethene and alpha-olefin copolymer produce has under identical melt index and density, and the physical performance index such as tensile strength (comprising surrender and breaking tenacity), the impact of becoming thin that characterize olefin polymer are improved all greatly.
Accompanying drawing explanation
Fig. 1 is axial location point distribution schematic diagram in fluidized-bed reactor in the present invention.
Embodiment
Term " melt index " refers to the melt flow rate (MFR) measured according to the GB/T-3682-2000 condition load of 2.16kg (190 DEG C), and is usually designated as MI
2.16.
The density of olefin polymer is measured according to GB/1033-1986 method.
Measure thickness according to GB/T1040.1-2006 method, use the method for GB/T1040.1 to measure the tensile strength of polymkeric substance.
According to the A method test dart drop value in GB/T9639.1-2008 method.
Embodiment 1
Catalyst preparing: introduce method for preparing catalyst in patent application WO2008/116396A1 and prepare catalyzer in the present embodiment.The first step prepares Ziegler-Natta catalyst (ZN-1) by Mg/Ti=5: 1; mould material is carried on described Ziegler-Natta catalyst by second step; (ZN-2) is carried on described rete by the 3rd step, and the 4th step is by stand-by except storing under desolventizing, nitrogen protection for described composite catalyst drying.
Prepared by polymkeric substance: be 3 meters at a diameter, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, 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.Polymeric reaction temperature 88 DEG C.The concentration 300ppm of promotor triethyl aluminum is added in reactor, then start catalyzer feeding equipment and the catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, start cryogen transferpump to add iso-pentane to reactor, control or to regulate in circulation gas iso-pentane concentration at 10.20%v/v all the time, make the dew point of the circulation gaseous stream outside reactor be elevated between 66 ~ 68 DEG C, close to or reach the boiling point 68.3 DEG C of hexene-1.Then, progressively regulate catalyzer to add intake rate between 2.0 ~ 2.2kg/hr, to control space-time yield make circulation gas at reactor inlet temperature between 40 ~ 43 DEG C, now recycle gas is compressed and is cooled 20 ~ 26%wt that rear generation liquids flow accounts for recycle gas total amount, these liquid are ejected through by vapor phase stream the grid distributor being arranged on reactor bottom and enter reactor lower part, the dew point of fluidisation gaseous stream is elevated between 66 ~ 75 DEG C, makes alkene polyreaction at this temperature.It should be noted that, the temperature of reaction in reactor in most of volume is 88 DEG C, but the polymeric reaction temperature of this zone of convergency and low-temperature region is 66 ~ 75 DEG C, and this low-temperature region is roughly 2m At The Height above grid distributor to grid distributor.
From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 2.The physical data of the respective films product using this olefin polymer to prepare also lists in table 2.In table 1 be the olefinic polyreaction in each embodiment and comparative example reactor in operational condition.
Embodiment 2
Catalyst preparing is with embodiment 1.
Prepared by polymkeric substance: be 3 meters at a diameter, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, 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.Polymeric reaction temperature 88 DEG C.The concentration 300ppm of promotor triethyl aluminum is added in reactor, then start catalyzer feeding equipment and the catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, start cryogen transferpump to add iso-pentane to reactor, control or to regulate in circulation gas iso-pentane concentration at 8.50%v/v all the time, make the dew point of the circulation gaseous stream outside reactor be elevated between 66 ~ 68 DEG C, close to or reach the boiling point 68.3 DEG C of hexene-1.Then, progressively regulate catalyzer to add intake rate between 2.0 ~ 2.2kg/hr, to control space-time yield make circulation gas at reactor inlet temperature between 40 ~ 43 DEG C, now recycle gas is compressed and is cooled 20 ~ 26%wt that rear generation liquids flow accounts for recycle gas total amount, these liquid are separated by pipe separator, be pressurized to 1.2Mpa with impeller pump again squeeze into the At The Height of the above 0.5m of reactor distributing plate and to spray in injecting reactor and the dew point of fluidisation gaseous stream is elevated between 66 ~ 73 DEG C, make alkene polyreaction at this temperature.Wherein, the low-temperature region of 66 ~ 73 DEG C is roughly 2.5m At The Height above grid distributor to grid distributor.
From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 2.The physical data of the respective films product using this olefin polymer to prepare also lists in table 2.
Embodiment 3
Catalyst preparing is with embodiment 1.
Prepared by polymkeric substance: be 3 meters at a diameter, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, 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.Polymeric reaction temperature 88 DEG C.The concentration 300ppm of promotor triethyl aluminum is added in reactor, then start catalyzer feeding equipment and the catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, start cryogen transferpump to add iso-pentane to reactor, control or to regulate in circulation gas iso-pentane concentration at 9.0%v/v all the time, make the dew point of the circulation gaseous stream outside reactor be elevated between 66 ~ 68 DEG C, close to or reach the boiling point 68.3 DEG C of hexene-1.Then, progressively regulate catalyzer to add intake rate between 2.0 ~ 2.2kg/hr, to control space-time yield make circulation gas at reactor inlet temperature between 40 ~ 43 DEG C, now recycle gas is compressed and is cooled 20 ~ 26%wt that rear generation liquids flow accounts for recycle gas total amount, these liquid are separated by pipe separator, be pressurized to 1.2Mpa with impeller pump again squeeze into two At The Heights of above 1.0m and 3.0m of reactor distributing plate and to spray in injecting reactor and the dew point of fluidisation gaseous stream is elevated between 66 ~ 73 DEG C, make alkene polyreaction at this temperature.Wherein, the low-temperature region of 66 ~ 73 DEG C is roughly 5m At The Height above grid distributor to grid distributor.
From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 2.The physical data of the respective films product using this olefin polymer to prepare also lists in table 2.
Embodiment 4
Catalyst preparing is with embodiment 1.
Prepared by polymkeric substance: be 3 meters at a diameter, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, 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.Polymeric reaction temperature 88 DEG C.The concentration 300ppm of promotor triethyl aluminum is added in reactor, then start catalyzer feeding equipment and the catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr, when reactor internal olefin polymerization exotherm, start cryogen transferpump to add iso-pentane to reactor, control or to regulate in circulation gas iso-pentane concentration at 10.05%v/v all the time, make the dew point of the circulation gaseous stream outside reactor be elevated between 66 ~ 68 DEG C, close to or reach the boiling point 68.3 DEG C of hexene-1.Then, progressively regulate catalyzer to add intake rate between 2.0 ~ 2.2kg/hr, to control space-time yield make circulation gas at reactor inlet temperature between 40 ~ 43 DEG C, now recycle gas is compressed and is cooled 20 ~ 26%wt that rear generation liquids flow accounts for recycle gas total amount, these liquid are separated by pipe separator, be pressurized to 1.2Mpa with impeller pump again and squeeze into the above 0.5m of reactor distributing plate, three At The Heights of 1.0m and 3.0m also spray in injecting reactor, and make the dew point of fluidisation gaseous stream be elevated between 66 ~ 74 DEG C, make alkene polyreaction at this temperature.Wherein, the low-temperature region of 66 ~ 74 DEG C is roughly 5m At The Height above grid distributor to grid distributor.
From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 2.The physical data of the respective films product using this olefin polymer to prepare also lists in table 2.
Comparative example 1
Catalyst preparing is with embodiment 1.
Prepared by polymkeric substance: poly-unit is identical with embodiment 1, and difference is that traditionally (temperature in whole gas-phase fluidized-bed reactor is same temperature) operates olefine polymerization reactor of gas phase fluidized bed.A diameter be 3 meters, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, with hexene-1 for comonomer produces agricultural greenhouse film product, reactant consists of: ethene 30.78%v/v, hexene-1 concentration 4.91%v/v, hydrogen 4.30%v/v.Polymeric reaction temperature 88 DEG C, adds 300ppm promotor triethyl aluminum in reactor, then starts catalyzer feeding equipment and the catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr.Catalyzer is progressively regulated to add intake rate between 2.0 ~ 2.2kg/hr, control space-time yield and make circulation gas at reactor inlet temperature at 38 ~ 41 DEG C, circulation gas dew point is at 48 ~ 50 DEG C, and now recycle gas is compressed and cools 3 ~ 7%wt that rear generation liquids flow accounts for recycle gas total amount.From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 2.The physical data of the respective films product using this olefin polymer to prepare also lists in table 2.
Comparative example 2
Catalyst preparing is with embodiment 1.
Prepared by polymkeric substance: poly-unit is identical with embodiment 1, and difference is that traditionally (temperature in whole gas-phase fluidized-bed reactor is same temperature) operates olefine polymerization reactor of gas phase fluidized bed.A diameter be 3 meters, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, be that comonomer produces 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.Polymeric reaction temperature 88 DEG C, adds 300ppm promotor triethyl aluminum in reactor, then starts catalyzer feeding equipment and the catalyzer of above-mentioned configuration is added reactor by the flow rate of 1.0kg/hr.Catalyzer is progressively regulated to add intake rate between 2.0 ~ 2.2kg/hr, control space-time yield and make circulation gas at reactor inlet temperature at 38 ~ 41 DEG C, circulation gas dew point is at 48 ~ 50 DEG C, and now recycle gas is compressed and cools 3 ~ 7%wt that rear generation liquids flow accounts for recycle gas total amount.From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 2.The physical data of the respective films product using this olefin polymer to prepare also lists in table 2.
Table 1
Table 2
As can be seen from Table 2, in embodiment, the melt index of polymkeric substance is similar with density to the melt index of polymkeric substance in comparative example with density; But during by the method for the invention operating fluidized bed reactor, after the polymkeric substance being polymerized generation under the gas dewpoint that reaction monomers is set up in reactor makes film article, the physicals such as impact of becoming thin, surrender breaking tenacity of film has great improvement.In addition, only there is the olefinic polymerization of smaller portions volume to carry out under dew-point temperature in embodiment 1 in reactor, and make in reactor, have the olefinic polymerization of comparatively large vol to carry out under dew-point temperature from three At The Height spraying liquids of grid distributor in reactor above 0.5m, 1.0m and 3.0m in embodiment 4; Become excellent gradually from the result of embodiment 1 to embodiment 4, illustrate that the low-temperature region volume reacted under dew-point temperature along with olefinic polymerization in reactor is larger, the physicals improvement of olefin polymer is more obvious.
Claims (11)
1. one kind utilizes fluidized-bed reactor to prepare the method for olefin polymer, it is characterized in that: the temperature in control flow check fluidized bed reactor, make in reactor, at least to there is a low-temperature region, its polymeric reaction temperature close to or equal the dew-point temperature of fluidizing agent in reactor, be specially two temperatures value difference ± 5 DEG C;
In circulation gas, add cryogen, it is 60 ~ 78 DEG C that the dew-point temperature of described fluidizing agent in reactor is raised.
2. method according to claim 1, is characterized in that: two temperatures value difference ± 3 DEG C.
3. method according to claim 1, is characterized in that: the dew-point temperature of described fluidizing agent is 66 ~ 75 DEG C.
4. method according to claim 1, is characterized in that: described cryogen be selected from ethane, propane, butane, pentane and hexane one or more.
5. method according to claim 4, is characterized in that: described cryogen is selected from pentane, hexane or its mixture.
6. method according to claim 1, is characterized in that: the subregion of described low-temperature region in reactor above grid distributor in 0 ~ 6m.
7. according to method described in any one in claim 1 ~ 6, it is characterized in that: the low-temperature region volume in reactor is 1/48 ~ 4/5 of whole reactor volume.
8. method according to claim 6, is characterized in that: the low-temperature region volume in reactor is 1/6 ~ 1/2 of whole reactor volume.
9. according to method described in any one in claim 1 ~ 6, it is characterized in that: preparing polymkeric substance catalyzer used is one or more in Ziegler-Natta catalyst, metallocene catalyst, and use triethyl aluminum is promotor.
10. according to method described in any one in claim 1 ~ 6, it is characterized in that: use alkene homopolymerization or copolymerization to prepare described polymkeric substance, wherein alkene comprises ethene, butene-1, hexene-1, octene-1.
11. methods according to claim 10, is characterized in that: use ethene and hexene-1 or octene-1 copolymerization.
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| EP3418308B1 (en) * | 2017-06-20 | 2020-03-11 | Borealis AG | A method, an arrangement and use of an arrangement for olefin polymerisation |
| 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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| CN1404491A (en) * | 2000-03-31 | 2003-03-19 | 三井化学株式会社 | Process for producing polyolefin composition |
| CN1976956A (en) * | 2004-05-20 | 2007-06-06 | 尤尼威蒂恩技术有限责任公司 | Gas olefin polymerization process |
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| CN1976956A (en) * | 2004-05-20 | 2007-06-06 | 尤尼威蒂恩技术有限责任公司 | Gas olefin polymerization process |
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