CN103387628B - A kind of system and method for olefinic polymerization - Google Patents
A kind of system and method for olefinic polymerization Download PDFInfo
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Abstract
The invention provides a kind of system and method for olefinic polymerization.Wherein system, comprises the reactor of more than three that are connected in series; First reactor is one or more annular-pipe reactor; Second reactor is one or more stirred-tank reactor; 3rd reactor is one or more gas-phase fluidized-bed reactor; Catalyzer and reaction mass enter the first reactor and carry out polyreaction, and the reaction product with catalyzer enters the second reactor, and supplementary material adds the second reactor, reacts; The reaction product of the second reactor outlet enters the 3rd reactor, and supplementary material adds the 3rd reactor, reacts, and finally in the 3rd reactor, is obtained by reacting final product.System and method of the present invention is for the production of the ultra-wide molecular weight distribution polyolefin with very good mechanical properties and processing characteristics.
Description
Technical field
The present invention relates to a kind of field of macromolecule polymerization, say further, relate to a kind of system and method for olefinic polymerization.
Background technology
The processing characteristics of polyolefin resin and mechanical property are conflicting, improve the raising that molecular weight contributes to the mechanical property of resin, but the processing of resin also can be made to become difficulty simultaneously.And broad peak (sometimes also referred to as bimodal or multimodal) polyolefin resin can realize the balance of materials processing performance and mechanical property, low molecular weight part wherein can ensure that resin has good processing characteristics, high molecular weight moieties gives the mechanical property of material simultaneously, as high tensile property, high tenacity and shock strength etc.Reactors in series combination process produces the most widely used industrial method with broad peak molecular weight distribution polyolefin resin at present, this method is under the reaction conditions formed at two or more gas with various, make alkene recur polyreaction, produce the polyolefin resin with broad peak molecular weight distribution.
A kind of series reactor process known in the art is the technique of slurry-phase reactor+slurry-phase reactor.The combination process carrying out olefinic polymerization in the slurry loop reactor of at least two series connection that such as CN101790544A and CN200580033634.6 mentions, and the method for producing bimodal polyethylene in two slurry reaction stills mentioned in CN1903896A.Above technique is all separated light constituent in the first reactor outlet slurry and polymkeric substance by flasher or fractionation plant.These class methods adopt slurry-phase reactor in the second reactor, and the amount of comonomers added is subject to the restriction of reactor fouling, and can not the higher product of production co-monomer content, and this just the second reactor produce a kind of requirement of high molecular weight products.Meanwhile, owing to only can provide two kinds of reaction conditionss, the molecular weight distribution of product can only present so-called bimodal form.
Another kind of known series reactor process is two gas-phase reactor processes.Two gas-phase reactor processes of the use series connection such as, mentioned in EP-A-691353 and US4420592, wherein the product of the first reactor is delivered to the second reactor by nitrogen.The problem that such technique runs into is that the first reactor adopts Gas-phase reactor, the impact of reactor and line of pipes is easily blocked by reaction product, this type of reactor is not suitable for producing low-molecular-weight product, and the target product of the first reactor when this produces broad peak distribution of products just.
The technique of this area also known a kind of slurry-phase reactor+Gas-phase reactor.The polyethylene multistage production technique such as, mentioned in EP0517868 and CN1708515A, wherein first paragraph is slurry polymerization in a loop reactor under super critical condition, and second segment carries out vapour phase polymerization in one or more Gas-phase reactor.To need the effluent flash distillation of the first reactor in this processing method, to the degree of " substantially removing all residual solution ", thus to need a large amount of energy.In addition, do not mention in the method if reclaimed efficiently " residual solution " that flash off.
CN101400933A discloses and a kind ofly in three reactors be connected in series, carries out suspension polymerization, produces " multi-modal " polyethylene molding composition (i.e. the polymkeric substance of a kind of multimodal or broad peak molecular weight distribution).This composition is made up of the ethylene copolymer of low-molecular-weight Alathon, high molecular and the ethylene copolymer of ultra-high molecular weight.This composition is compared with foregoing bimodal polyethylene, and its mechanical property particularly environment resistant stress rupture and notched impact strength has had significant raising.But owing to still adopting slurry reaction in this patent in the end first order reaction, compared with gas-phase reaction, the material that during reaction discharging, the needs of entrained with reclaim is more, is separated and reclaims comparatively difficulty, big energy-consuming and need increase investment.
CN101035851A also refer to a kind of preparation method of multimodal polyethylene composition, and this composition comprises ethylene homo or the co-polymeric share that three have different weight-average molecular weight.Its preferred implementation realizes in pre-polymerization annular-pipe reactor, annular-pipe reactor and the fluidized-bed reactor described in EP0517868.The deficiency of its polymerization technique is identical with foregoing EP0517868 with CN1708515A.
Therefore, need to find the gentle polyolefin process comprising more than three or three reactors be in series of a kind of more economic and reliable slurries, for the production of the product of ultra-wide molecular weight distribution.
Summary of the invention
For the problems of the prior art, the object of this invention is to provide a kind of system and method for olefinic polymerization.The system and method for this olefinic polymerization, can the polyolefine of production ultra-wide molecular weight distribution, and production cost is lower, flow process more rationally, more energy-conservation.
An object of the present invention is to provide a kind of system of olefinic polymerization, it comprises the reactor of more than three that are connected in series.Wherein, the first reactor is one or more annular-pipe reactor; Second reactor is one or more stirred-tank reactor; 3rd reactor is one or more gas-phase fluidized-bed reactor; Reaction mass enters the first reactor and carries out polyreaction, and the reaction product with catalyzer enters the second reactor, and supplementary material adds the second reactor, reacts; The reaction product of the second reactor outlet enters the 3rd reactor, and supplementary material adds the 3rd reactor, reacts, and finally in the 3rd reactor, is obtained by reacting final product.Above-mentioned reaction mass comprises catalyzer, thinner and reaction raw materials etc.; Supplement material, comprise catalyzer, thinner, reaction raw materials etc. that needs supplement.Wherein reaction raw materials refers to monomer (comprise polymerization single polymerization monomer, or polymerization single polymerization monomer and comonomer), hydrogen.
In order to improve reaction efficiency, reducing energy and material consumption, being preferably outside equipped with separating unit at the second reactor; 3rd reactor is outside equipped with knockout drum.Catalyzer and reaction mass enter the first reactor and carry out polyreaction, and the reaction product with catalyzer enters the second reactor, supplement material and add the second reactor together with the liquid phase from separating unit, react simultaneously; The reaction product of the second reactor outlet enters the 3rd reactor, and the circulation gas of the 3rd reactor outlet enters gas-liquid separator, and the gas phase separated and supplementary mixing of materials enter the 3rd reactor, and are obtained by reacting final product in the 3rd reactor; The gas evaporated in second reactor enters separating unit, and here contact with the liquid phase discharging of gas-liquid separator, isolate light, weigh two kinds of components, heavy constituent (containing thinner, comonomer) returns the second reactor so that liquid form is all or part of, and light constituent goes aftertreatment recovery system with gas phase.
At the second reactor of present system, namely in stirred-tank reactor, the heat that the polyreaction occurred in reactor produces can be utilized, make to enter light constituent flash separation in the first reactor effluent of reactor and be separated with polymer slurries, thus realization response and the coupling be separated in a reactor.
Described separating unit can comprise one or two above rectifying tower, for separating of the component gone out required for the second reactor and unwanted component, and the component needed, namely according to the component maintained needed for reactant concn, return the second reactor in the desired amount.A kind of preferred version is the rectifying tower adopting at least one band lateral line discharging, with simple flow, minimizing equipment: when comonomer is heavier than thinner, comonomer and thinner are gone out from tower bottom flow, loop back second or the 3rd reactor as required, at side take-off substantially not containing the thinner of copolymerization component, loop back the first reactor, be rich in the light constituent of alkene and hydrogen from overhead extraction, see accompanying drawing 2; When comonomer is lighter than thinner, its lateral line discharging (higher than the comonomer concentration at the bottom of tower) enters the 3rd reactor, the amount of comonomers entering the second reactor is controlled like this by lateral line discharging amount, discharging at the bottom of tower is mainly thinner, the second or first reactor can be looped back as required, overhead extraction is rich in the light constituent of alkene and hydrogen, sees accompanying drawing 3.
By selecting rational separating unit, necessary being separated being carried out to heavy constituent (containing thinner, comonomer) and light constituent, makes the operation between the second reactor and the 3rd reactor relatively independent.Meanwhile, control the amount of the comonomer entered in the second reactor, the second reactor is operated under required reactant concn, finally realizes the control to the polyolefin products quality of producing in the second reactor.
So, as compared to two gas-phase reactor processes that the use mentioned in EP-A-691353 with US4420592 is connected, due to adding of the second reactor in system of the present invention and separating unit, make the operational condition of each reactor relatively independent, avoid material between reactor that two gas-phase reactor processes runs into and there is the problem of altering mutually.As compared to the tandem process of the annular-pipe reactor+Gas-phase reactor mentioned in EP0517868 with CN1708515A, utilize polyreaction heat release that light constituent is evaporated, avoid the separation using the high pressure flash method of high energy consumption to carry out light constituent, there is good energy-saving effect.
In system of the present invention, the effluent (reaction product) of the second reactor keeps the state of its slurries directly to enter the 3rd reactor (gas-phase fluidized-bed reactor), the liquid evaporation contained in effluent may be used for the reaction heat removing the 3rd reactor, this is identical with the what is called " condensation process " described in patent CN1171793, can improve the space-time yield of the 3rd reactor.
In addition, particularly, the reaction product slurry of described first reactor enters the second reactor after reducing valve decompression and First Heat Exchanger heat exchange; The outlet circulation gas of the 3rd reactor enters gas-liquid separator through the second interchanger; Gas-liquid separator separates gas phase is out through compressor compression and supplement mixing of materials, enters the 3rd reactor.
According to system of the present invention, second object of the present invention is to provide a kind of method of olefinic polymerization, and it comprises the following steps:
1) make to comprise olefinic polymerization monomer, catalyzer the raw material of polyreaction in described first reactor, be polymerized under the first reactant concn existent condition, output is with the reaction product of catalyzer;
2) reaction product with catalyzer of above-mentioned first reactor output enters described second reactor; In the second reactor, with the supplementary material added, form the second reactant concn, the reaction product of output second reactor;
3) reaction product of above-mentioned second reactor enters described 3rd reactor, is polymerized, obtains polyolefin products with supplementary material under the condition of the third formed reactant concn.
Described forming reactions substrate concentration refers to the reaction product quantity by adjustment turnover reactor, makes the reactant concn in reactor reach the predetermined requirement of polyreaction.
Preferably, described step 2) in, the reaction product with catalyzer of the first reactor output enters described second reactor, and isolate the gas that decompression process obtains, gas enters separating unit; The reaction product stayed, with the supplementary material added, and forms the second reactant concn together from the liquid phase of separating unit;
In described step 3), the reaction product of the second reactor enters described 3rd reactor, the circulation gas of the 3rd reactor outlet enters gas-liquid separator, the gas phase separated and supplementary mixing of materials, enter the 3rd reactor, be polymerized under the condition of the third formed reactant concn, obtain polyolefin products.
The reaction product of described first reactor enters the second reactor after decompression and heat exchange; The outlet circulation gas of the 3rd reactor enters gas-liquid separator through heat exchange; Compressed and the supplementary mixing of materials of gas-liquid separator separates gas phase out, enters the 3rd reactor.
The method of olefinic polymerization of the present invention, polymerization process condition in its each reactor, comprise temperature, pressure etc., used reaction raw materials (comprising polymerization single polymerization monomer, comonomer, hydrogen), thinner, catalyzer etc. and consumption etc., wait and all adopt olefinic polymerization in prior art to commonly use polymerization process condition.
Specifically, polymerization single polymerization monomer described in olefine polymerizing process of the present invention is the monoolefine of C2 ~ C4, preferred C2, preferably includes comonomer in the supplementary material in described second reactor and the 3rd reactor, described comonomer is the alkene or derivatives thereof of C3 ~ C8, preferred hexene-1.Comonomer wherein in the second reactor and polymerization single polymerization monomer mol ratio are 0.001 ~ 1.Comonomer in 3rd reactor and polymerization single polymerization monomer mol ratio are 0.001 ~ 0.2, are preferably 0.01 ~ 0.1, and the comonomer be greater than in the second reactor and polymerization single polymerization monomer mol ratio.
The thinner used in first reactor and the second reactor, is selected from least one in propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane, preferred Trimethylmethane.
In the method for the invention, carry out condensation or super condensation operation at the 3rd reactor, to improve the space-time yield of reactor, what increase reactor removes heat energy power.The induced condensing agent wherein introduced is unreactive hydrocarbons, and described unreactive hydrocarbons are selected from least one in Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane.In 3rd reactor, adding of induced condensing agent removes heat problem to solve polyreaction better, and in the first reactor and the second reactor adding of thinner be the flowability problem improving polymeric reaction product.If induced condensing agent and thinner adopt same substance, then corresponding tripping device need not be set and be separated, can process be simplified.Therefore, the material that induced condensing agent is preferably identical with thinner in the first reactor.
Catalyzer in described first reactor is selected from least one in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse;
Add in described second reactor and the 3rd reactor or do not add catalyzer;
When adding catalyzer in the second reactor and the 3rd reactor, this catalyzer is selected from least one in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse.
The method of olefinic polymerization of the present invention, containing higher hydrogen in the first reactant concn in described first reactor, consequently the molecular weight of the first reactor effluent is lower; And under the second reactant concn and the 3rd reactant concn condition, produce olefin copolymer respectively at described second reactor and the 3rd reactor.Hydrogen wherein in the first reactor/polymerization single polymerization monomer mol ratio is 0.05 ~ 2, preferably 0.1 ~ 0.6; Hydrogen in second reactor/polymerization single polymerization monomer mol ratio is 0 ~ 0.5, is preferably 0, i.e. not hydrogenation; Hydrogen/polymerization single polymerization monomer the mol ratio of the 3rd reactor is 0.0001 ~ 0.1, and is preferably less than the hydrogen/polymerization single polymerization monomer mol ratio of the first reactor.
The service temperature of described first reactor is 20 ~ 130 DEG C, preferably 75 ~ 115 DEG C; Working pressure is 0.1 ~ 10.0MPa, preferably 3.0 ~ 5.0MPa.The service temperature of described second reactor is 60 ~ 95 DEG C, preferably 70 ~ 85 DEG C; Working pressure is 0.1 ~ 2.0MPa, preferably 0.7 ~ 1.6MPa.The service temperature of described 3rd reactor is 60 ~ 130 DEG C, preferably 70 ~ 110 DEG C; Working pressure is 1.0 ~ 4.0MPa, preferably 1.0 ~ 2.5MPa.
In described separating unit, the working pressure of rectifying tower is at 0.1 ~ 2MPa, preferably close with the pressure of the second reactor; Temperature condition is at the bottom of tower 65 ~ 90 DEG C, tower top 35 ~ 50 DEG C.
One of preferred version of method of the present invention is in the first reactor, produce the low-molecular-weight polyolefine of high-density; The polyolefine of low density high molecular is produced in the 3rd reactor; And in the second reactor the marginal polyolefine of production melting index, produce " fused layer " part crucial between bimodal distribution, assign to avoid high molecular or low molecular weight part to be separated in post-treatment process with appropriate pars intermedia, and this series products is called the polyolefine of first kind ultra-wide molecular weight distribution.When adopting this preferred version, the service temperature of the second reactor preferably 80 ~ 85 DEG C, working pressure is 0.7 ~ 1.6MPa; To be the hydrogen/polymerization single polymerization monomer mol ratio of preferably the 0.01 ~ 0.1, three reactor be preferably 0.0001 ~ 0.001 for hydrogen and polymerization single polymerization monomer mol ratio.
Another preferred version of method of the present invention is the low-molecular-weight polyolefine of production high-density in the first reactor; The polyolefine of low density high molecular is produced in the 3rd reactor; And in the second reactor the polyolefine of production ultra-high molecular weight, the product of gained is Equations of The Second Kind ultra-wide molecular weight distribution polyolefin, and its mechanical property particularly environment resistant stress rupture and notched impact strength has had significant raising.When adopting this preferred version, the service temperature of the second reactor preferably 70 ~ 75 DEG C, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio are that to be preferably the hydrogen/polymerization single polymerization monomer mol ratio of the 0, three reactor be preferably 0.001 ~ 0.01.
Above-mentioned preferred version is in order to the polyolefine how preparing required ultra-wide molecular weight distribution is described, but not limits the scope of the invention.
According to the present invention, more specifically olefinic polymerization flow process is as follows:
Catalyzer and reaction mass (polymerization single polymerization monomer, hydrogen etc.) enter the first reactor and annular-pipe reactor, and carry out polyreaction wherein.Reaction product slurry is after decompression and heat exchange, and the slurries with catalyzer enter the second reactor and stirred-tank reactor.The liquid phase discharging of the supplementary material containing comonomer and separating unit also simultaneously together with add the second reactor and react.The gas evaporated in second reactor enters separating unit, and here contacts with the liquid phase discharging of gas-liquid separator, is separated thinner, comonomer and light constituent.The outlet slurry of the second reactor enters the 3rd reactor and gas-phase fluidized-bed reactor.The circulation gas of the 3rd reactor outlet enters gas-liquid separator after heat exchange cooling, with supplementary mixing of materials after the compressed pressurization of the gas phase separated, enters the 3rd reactor, and be obtained by reacting final product in the 3rd reactor.
Now multiple steps of the inventive method are described in detail:
A. the first reactor
Described first reactor, namely in annular-pipe reactor, carries out the homopolymerization of olefinic polymerization monomer as ethene in inert hydrocarbon diluent.Described inert hydrocarbon diluent is selected from propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane and their mixture, preferred Trimethylmethane.The service temperature of annular-pipe reactor is 20 ~ 130 DEG C, preferably 70 ~ 115 DEG C, more preferably 85 ~ 110 DEG C; Working pressure is 0.1 ~ 10.0MPa, preferably 3.0 ~ 5.0MPa.Hydrogen/monomer mol ratio in reactor is 0.05 ~ 2, preferably 0.1 ~ 0.6.Selected catalyzer can be Ziegler-Natta catalyst, metallocene catalyst or the centers catalyse agent of Nonmetallocene monomer and their mixture.
The low-molecular-weight polymkeric substance of high-density is produced, its melting index MI in the first reactor
2.16between 2 ~ 500g/10min or higher, density is at 935kg/m
3above.
B. the second reactor
Described first reactor effluent enters the second reactor through reducing valve and First Heat Exchanger, i.e. stirred-tank reactor, carries out alkene as ethene in inert hydrocarbon diluent, with the copolyreaction of comonomer as hexene-1.Described inert hydrocarbon diluent is selected from propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane and their mixture, preferred Trimethylmethane.The service temperature of stirred-tank reactor is 60 ~ 95 DEG C, preferably 70 ~ 85 DEG C; Working pressure is 0.1 ~ 2.0MPa, preferably 0.7 ~ 1.6MPa.Select in reactor to add or not hydrogenation, hydrogen when adding hydrogen in reactor and polymerization single polymerization monomer mol ratio are 0 ~ 0.5.Comonomer and polymerization single polymerization monomer mol ratio are 0.001 ~ 1.Selected catalyzer can be Ziegler-Natta catalyst, metallocene catalyst or the centers catalyse agent of Nonmetallocene monomer and their mixture, or no longer adds new catalyzer.
The heat utilizing polyreaction to produce in the second reactor, make the light constituent flash distillation entering reactor, realization is separated with polymer slurries, thus realization response and the coupling be separated in a reactor, make the operation of the first reactor and the 3rd reactor relatively independent.
The polymericular weight of producing in the second reactor has multiple choices.Wherein preferred version produces crucial " fused layer " part between bimodal distribution, assigns to avoid high molecular or low molecular weight part in post-treatment process " precipitation " with appropriate pars intermedia.A kind of preferred version is the polyolefine of production ultra-high molecular weight in addition, significantly to improve polyolefinic processing characteristics and mechanical property.
C. the 3rd reactor
Described second reactor effluent enters the 3rd reactor, i.e. gas-phase fluidized-bed reactor.The operational condition of this reactor is substantially identical with conventional fluidized-bed reactor, its operating temperature range about 60 ~ 130 DEG C, preferably 70 ~ 110 DEG C; Working pressure scope 1.0 ~ 4.0MPa, preferably 1.5 ~ 2.5MPa.The hydrogen/monomer mol ratio of the 3rd reactor is 0.0001 ~ 0.1 and is preferably less than the hydrogen/monomer mol ratio of the first reactor.Comonomer in 3rd reactor and polymerization single polymerization monomer mol ratio are 0.001 ~ 0.2, and the mol ratio of preferred comonomers and polymerization single polymerization monomer is be 0.01 ~ 0.1 and the mol ratio of the comonomer be greater than in the second reactor and polymerization single polymerization monomer.Selected catalyzer can be Ziegler-Natta catalyst, metallocene catalyst or the centers catalyse agent of Nonmetallocene monomer and their mixture, or no longer adds new catalyzer.
Can use condensation or super condensation operation in described 3rd reactor, to improve the space-time yield of reactor, what increase reactor removes heat energy power.Condensation or supercool coagulate manipulation require and introduce one or more unreactive hydrocarbons, such as Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane and their mixture, preferably identical with thinner in the first reactor material.
The polymkeric substance of low density high molecular is produced, its melting index MI in the 3rd reactor
21.6at below 50g/10min, density is at 935kg/m
3below.The polyolefine of the ultra-wide molecular weight distribution finally generated by the 3rd reactor interval or continuous print discharging.
D. separating unit
Described separating unit can be one or more rectifying tower, and for separating of the component gone out required for the second reactor and unwanted component, and the component needed returns the second reactor.Relevant flow process is described below: the circulation gas of the 3rd reactor entered after the second interchanger cools to enter gas-liquid separator, the liquid phase discharging of gas-liquid separator contacts with the vaporised gas of the second reactor in separating unit, reclaim thinner in vaporised gas as Trimethylmethane, separating unit liquid phase discharging recycle as required.
A kind of preferred version of separating unit is the rectifying tower using at least one band side take-off.The working pressure of tower can at 0.1 ~ 2MPa, preferably close with the pressure of the second reactor.Preferred temperature condition is at the bottom of tower 65 ~ 90 DEG C, tower top 35 ~ 50 DEG C.In actually operating, when comonomer is heavier than thinner, comonomer and thinner are gone out from tower bottom flow, loop back second or the 3rd reactor as required, at side take-off substantially not containing the thinner of copolymerization component, loop back the first reactor, be rich in the light constituent of alkene and hydrogen from overhead extraction, see accompanying drawing 2; When comonomer is lighter than thinner, its lateral line discharging (higher than the comonomer concentration at the bottom of tower) enters the 3rd reactor, the amount of comonomers entering the second reactor is controlled like this by lateral line discharging amount, discharging at the bottom of tower is mainly thinner, the second or first reactor can be looped back as required, overhead extraction is rich in the light constituent of alkene and hydrogen, sees accompanying drawing 3.
By regulating the separating power of separating unit, controlling the amount of the comonomer entered in the second reactor, making the operation between the second reactor and the 3rd reactor relatively independent, and the control to the polyolefin products quality of producing in the second reactor can be realized.
Utilize method of the present invention, the polyolefine, particularly polyethylene of the ultra-wide molecular weight distribution with very good mechanical properties and processing characteristics can be produced.The polyolefine of so-called ultra-wide molecular weight distribution, refers to that molecular weight distribution is wider than common bimodal polyolefin, and has some special part to strengthen polyolefinic processing characteristics and/or mechanical property.This area adopts polydispersity coefficient PDI to weigh the width of polyolefin molecular weight distribution usually.Polydispersity coefficient PDI is defined as the ratio of weight-average molecular weight Mw and number-average molecular weight Mn, and polydispersity coefficient PDI is larger, and the molecular weight distribution of representation polymer is wider.The polyolefinic polydispersity coefficient of ultra-wide molecular weight distribution of the present invention is higher than common bimodal polyolefin, and its molecular weight distribution is greater than 10, is preferably greater than 15.
System and method of the present invention is applicable to vinyl polymerization, propylene polymerization or other olefinic polymerization, particularly preferably is and is applicable to vinyl polymerization.
The present invention compared with prior art has following outstanding feature and effect:
1., by the reaction conditions of control three reactors, produce the polyolefine with the ultra-wide molecular weight distribution of very good mechanical properties and processing characteristics.First reactor adopts slurry reaction, produces the product that molecular weight is lower, and the 3rd reactor adopts gas-phase reaction, the more product of convenient production comonomer.Wherein a kind of preferred version is the polyolefine of production melting index between the first reactor and the 3rd reactor in the second reactor, produce " fused layer " part crucial between bimodal distribution, assign to avoid high molecular or low molecular weight part to be separated in post-treatment process with appropriate pars intermedia; A kind of preferred version is the polyolefine of production ultra-high molecular weight in the second reactor in addition, significantly improves polyolefinic processing characteristics and mechanical property.
2. the second reactor in the present invention, stirred-tank reactor, play polyreaction and the effect being separated light constituent in the first reactor effluent, be a kind of device of simultaneous reaction and separation simultaneously, makes the operation between the first reactor and the 3rd reactor relatively independent simultaneously.The heat utilizing polyreaction to produce in the reactor, makes the light constituent flash distillation entering reactor, realizes and being separated of polymer slurries, thus realization response and the coupling be separated in a reactor, save the investment of equipment.
3. by regulating the separating power of described separating unit, control the amount of the comonomer entered in the second reactor, make the operation between the second reactor and the 3rd reactor relatively independent, and the control to the polyolefin products quality of producing in the second reactor can be realized.
4. can use condensation or super condensation operation in the 3rd reactor described in, to improve the space-time yield of reactor, what increase reactor removes heat energy power.
Accompanying drawing explanation
Fig. 1 olefin polymerization reaction unit schematic diagram of the present invention.
Fig. 2 separating unit of the present invention selects an olefin polymerization reaction unit schematic diagram being with side take-off rectifying tower.Its lateral line discharging enters the first reactor.
Fig. 3 separating unit of the present invention selects an olefin polymerization reaction unit schematic diagram being with side take-off rectifying tower.Its lateral line discharging enters the 3rd reactor.
Description of reference numerals:
1 first reactor 2 reducing valve 3 First Heat Exchanger
4 second reactor 5 impeller pump 6 the 3rd reactors
7 second interchanger 8 gas-liquid separator 9 compressors
10 separating units
Embodiment
Following examples are to further illustrate the present invention, but not limit the scope of the invention.
Olefinic polyreaction flow process is as shown in Figure 1 as follows: the reaction mass containing catalyzer enters the first reactor 1, annular-pipe reactor, and carries out polyreaction wherein.Reaction product slurry is after reducing valve 2 and First Heat Exchanger 3, and the slurries with catalyzer enter the second reactor 4, stirred-tank reactor.The liquid phase discharging of the supplementary material containing monomer and separating unit 10 rectifying tower also simultaneously together with add the second reactor 4 and react.In second reactor 4, the gas of evaporation enters separating unit 10, and here contacts with the liquid phase discharging of gas-liquid separator 8, is separated thinner, comonomer and light constituent.The outlet slurry of the second reactor 4 enters the 3rd reactor 6, gas-phase fluidized-bed reactor.3rd reactor 6 export circulation gas through second interchanger 7 cool after enter gas-liquid separator 8, the gas phase separated through compressor 9 pressurize after with supplement mixing of materials, enter the 3rd reactor 6, and be obtained by reacting final product in the 3rd reactor 6.
Embodiment 1
As shown in Figure 1, the polyethylene of production ultra-wide molecular weight distribution in the reactor of three series connection, output is 300,000 tons/year, and the productive rate of three reactors is assigned as 50:5:45.In described flow process, Ziegler-Natta catalyst and thinner Trimethylmethane, and ethene, hydrogen enter the first reactor 1---annular-pipe reactor, temperature of reaction 95 DEG C, pressure 4.0MPa together.Wherein the inlet amount of ethene is 19962kg/hr, regulates hydrogen feed amount, makes the hydrogen/ethylene molar ratio in slurries be 0.234.In reactor effluent, poly output is 18750kg/hr, and the massfraction in slurries shared by polymkeric substance is 45%.
After annular-pipe reactor effluent entered decompression, its temperature became 65 DEG C, and pressure is 1.25MPa, and formed containing the gas phase of 35.5%, then entered the second reactor 4---stirred-tank reactor.The temperature of reaction of this reactor is 75 DEG C, and pressure is 1.06MPa.Reactor fresh feed is only containing ethene, flow is 2554kg/hr, and control to enter the thinner Trimethylmethane of reactor and the amount of comonomer hexene-1 by separating unit 10, make hexene-1/ ethylene molar ratio in reactor in gas phase be 0.244, hydrogen/ethylene molar ratio is 0.106.In reactor effluent, poly flow is 20625kg/hr, and the massfraction in slurries shared by polymkeric substance is 34%.
Stirred-tank reactor effluent enters the 3rd reactor 6---and continue polymerization in gas-phase fluidized-bed reactor, temperature of reaction is 92 DEG C, and pressure is 2.0MPa.Gas-phase fluidized-bed reactor adopts condensation operation, and cryogen is Trimethylmethane.In circulation gas, hydrogen/ethylene molar ratio is 0.0300, and hexene-1/ ethylene molar ratio is 0.0525, and the volumetric molar concentration of cryogen Trimethylmethane is 26%.Reactor effluent is the polyethylene of described first kind ultra-wide molecular distribution, and its ultimate production is 37500kg/hr, and number-average molecular weight is 18007, and weight-average molecular weight is 330248, and molecular weight distributing index is 18.34.
Above-mentioned separating unit 10 can adopt the prioritization scheme (see accompanying drawing 2) of rectifying tower as separating unit being with lateral line discharging.Now, rectifying tower lateral line discharging enters the first reactor; Go the inventory of aftertreatment recovery system (being 25363kg/hr after optimizing) from separating unit 10, and the diluent mass flow (being 20710kg/hr after optimizing) adding the first reactor 1 can reduce 1300kg/hr respectively.And the operational condition of each reactor is constant, the finished product of same quality and quantity therefore can be obtained.
Embodiment 2
First reactor 1 is selected identical with embodiment 1 with the operational condition of the 3rd reactor 6 with material composition, and by regulating the separating power of middle separating unit 10, controlling the second reactor 4---the operational condition of stirred-tank reactor, realizes producing the poly object of Equations of The Second Kind ultra-wide molecular distribution.
The temperature of reaction of the second reactor is 75 DEG C, and pressure is 1.6MPa.Do not add comonomer in reactor, fresh feed is only containing ethene, and flow is 1098kg/hr, controls the amount entering the thinner Trimethylmethane of reactor, to ensure normally carrying out of slurry reaction by separating unit 10.Hydrogen/ethylene molar ratio in reactor is 0.106.In reactor effluent, poly flow is 20625kg/hr, and the massfraction in slurries shared by polymkeric substance is 43%.
Reactor effluent is the polyethylene of described Equations of The Second Kind ultra-wide molecular distribution, and its ultimate production is 37500kg/hr, and number-average molecular weight is 18136, and weight-average molecular weight is 411893, and molecular weight distributing index is 22.71.
Comparative example
Comparative example produces polyethylene in the double loop reactor of series connection.In described flow process, Ziegler-Natta catalyst and thinner Trimethylmethane, and ethene, hydrogen enter first ring pipe reactor, temperature of reaction 96 DEG C, pressure 4.2MPa together.Wherein the inlet amount of ethene is 17620kg/hr, regulates hydrogen feed amount, makes the hydrogen/ethylene molar ratio in slurries be 0.58.In reactor effluent, poly output is 17273kg/hr, and the massfraction in slurries shared by polymkeric substance is 46%.
First ring pipe reactor effluent entered the second annular-pipe reactor after entering the light constituents such as reduction vaporization removing hydrogen.Temperature of reaction is 84 DEG C, and pressure is 3.0MPa.Control feed composition, make the hydrogen/ethylene molar ratio in slurries be 0.00669, hexene-1/ ethylene molar ratio in reactor is 1.13.In reactor effluent, poly flow is 35961kg/hr, and the massfraction in slurries shared by polymkeric substance is 54%.Number-average molecular weight is 7219, and weight-average molecular weight is 75651, and molecular weight distributing index is 10.48.
Claims (22)
1. a system for olefinic polymerization, comprises the reactor of more than three that are connected in series, it is characterized in that:
First reactor is one or more annular-pipe reactor; Second reactor is one or more stirred-tank reactor; 3rd reactor is one or more gas-phase fluidized-bed reactor;
Reaction mass enters the first reactor and carries out polyreaction, and the reaction product with catalyzer enters the second reactor, and supplementary material adds the second reactor, reacts; The reaction product of the second reactor outlet enters the 3rd reactor, and supplementary material adds the 3rd reactor, reacts, and finally in the 3rd reactor, is obtained by reacting final product.
2. the system of olefinic polymerization as claimed in claim 1, is characterized in that:
Described second reactor is outside equipped with separating unit; Described 3rd reactor is outside equipped with knockout drum;
The circulation gas of described 3rd reactor outlet enters gas-liquid separator, and the gas phase separated and supplementary mixing of materials enter the 3rd reactor; The liquid phase separated is all or part of enters described separating unit; The gas evaporated in second reactor enters separating unit, and here contact with the liquid phase discharging of gas-liquid separator, isolate light, weigh two kinds of components, heavy constituent returns the second reactor so that liquid form is all or part of, and light constituent goes aftertreatment recovery system with gas phase.
3. the system of olefinic polymerization as claimed in claim 2, is characterized in that:
Described separating unit comprises one or more rectifying tower.
4. the system of olefinic polymerization as claimed in claim 3, is characterized in that:
In described rectifying tower, at least one is the rectifying tower of band lateral line discharging, and its lateral line discharging enters the first reactor or the 3rd reactor.
5. the system of the olefinic polymerization as described in any one of claim 2 ~ 4, is characterized in that:
The reaction product of described first reactor enters the second reactor after reducing valve decompression and First Heat Exchanger heat exchange; The outlet circulation gas of the 3rd reactor enters gas-liquid separator through the second interchanger; Gas-liquid separator separates gas phase is out through compressor compression and supplement mixing of materials, enters the 3rd reactor.
6. adopt a method for the olefinic polymerization of system as described in any one of Claims 1 to 5, it is characterized in that comprising the following steps:
1) make to comprise olefinic polymerization monomer, catalyzer the raw material of polyreaction in described first reactor, be polymerized under the first reactant concn existent condition, output is with the reaction product of catalyzer;
2) reaction product with catalyzer of above-mentioned first reactor output enters described second reactor; In the second reactor, with the supplementary material added, form the second reactant concn, the reaction product of output second reactor;
3) reaction product of above-mentioned second reactor enters described 3rd reactor, is polymerized, obtains polyolefin products with supplementary material under the condition of the third formed reactant concn.
7. the method for olefinic polymerization as claimed in claim 6, is characterized in that:
Described step 2) in, the reaction product with catalyzer of the first reactor output enters described second reactor, and isolate the gas that decompression process obtains, gas enters separating unit; The reaction product stayed, with the supplementary material added, and forms the second reactant concn together from the liquid phase of separating unit;
Described step 3) in, the reaction product of the second reactor enters described 3rd reactor, the circulation gas of the 3rd reactor outlet enters gas-liquid separator, the gas phase separated and supplementary mixing of materials, enter the 3rd reactor, be polymerized under the condition of the third formed reactant concn, obtain polyolefin products.
8. the method for olefinic polymerization as claimed in claim 6, is characterized in that:
The reaction product of described first reactor enters the second reactor after decompression and heat exchange; The outlet circulation gas of the 3rd reactor enters gas-liquid separator through heat exchange; Compressed and the supplementary mixing of materials of gas-liquid separator separates gas phase out, enters the 3rd reactor.
9. the method for the olefinic polymerization as described in any one of claim 6 ~ 8, is characterized in that:
Described polymerization single polymerization monomer is the monoolefine of C2 ~ C4;
Include comonomer in supplementary material in the second described reactor and the 3rd reactor, described comonomer is the alkene or derivatives thereof of C3 ~ C8;
Comonomer in the second wherein said reactor and the mol ratio of polymerization single polymerization monomer are 0.001 ~ 1;
Comonomer in the 3rd described reactor and the mol ratio of polymerization single polymerization monomer are 0.001 ~ 0.2.
10. the method for olefinic polymerization as claimed in claim 9, is characterized in that:
Described polymerization single polymerization monomer is C2 monoolefine;
Comonomer in the second described reactor and the 3rd reactor is hexene-1;
Comonomer in the 3rd described reactor and the mol ratio of polymerization single polymerization monomer are 0.01 ~ 0.1 and the mol ratio of the comonomer be greater than in the second reactor and polymerization single polymerization monomer.
The method of 11. olefinic polymerizations as claimed in claim 9, is characterized in that:
In reactant in the first described reactor, hydrogen and polymerization single polymerization monomer mol ratio are 0.05 ~ 2;
In reactant in the second described reactor, hydrogen and polymerization single polymerization monomer mol ratio are 0 ~ 0.5;
In reactant in the 3rd described reactor, hydrogen and polymerization single polymerization monomer mol ratio are 0.0001 ~ 0.1.
The method of 12. olefinic polymerizations as claimed in claim 11, is characterized in that:
Hydrogen in the first described reactor and polymerization single polymerization monomer mol ratio are 0.1 ~ 0.6;
Not hydrogenation in the second described reactor;
Hydrogen in the 3rd described reactor and polymerization single polymerization monomer mol ratio are less than hydrogen in the first reactor and polymerization single polymerization monomer mol ratio.
The method of 13. olefinic polymerizations as claimed in claim 9, is characterized in that:
The thinner used in first reactor and the second reactor is selected from least one in propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane.
The method of 14. olefinic polymerizations as claimed in claim 9, is characterized in that:
Described 3rd reactor carries out condensation or super condensation operation, and the induced condensing agent wherein introduced is unreactive hydrocarbons, and described unreactive hydrocarbons are selected from least one in Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane.
The method of 15. olefinic polymerizations as claimed in claim 14, is characterized in that:
Described induced condensing agent is identical material with thinner in the first reactor.
The method of 16. olefinic polymerizations as claimed in claim 9, is characterized in that:
Catalyzer in described first reactor is selected from least one in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse;
Add in described second reactor and the 3rd reactor or do not add catalyzer;
When adding catalyzer in the second reactor and the 3rd reactor, this catalyzer is selected from least one in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse.
The method of 17. olefinic polymerizations as claimed in claim 9, is characterized in that:
The service temperature of described first reactor is 20 ~ 130 DEG C; Working pressure is 0.1 ~ 10.0MPa;
The service temperature of described second reactor is 60 ~ 95 DEG C; Working pressure is 0.1 ~ 2.0MPa;
The service temperature of described 3rd reactor is 60 ~ 130 DEG C; Working pressure is 1.0 ~ 4.0MPa.
The method of 18. olefinic polymerizations as claimed in claim 17, is characterized in that:
The service temperature of described first reactor is 75 ~ 115 DEG C; Working pressure is 3.0 ~ 5.0MPa;
The service temperature of described second reactor is 70 ~ 85 DEG C; Working pressure is 0.7 ~ 1.6MPa;
The service temperature of described 3rd reactor is 70 ~ 110 DEG C; Working pressure is 1.0 ~ 2.5MPa.
The method of 19. olefinic polymerizations as claimed in claim 17, is characterized in that:
In separating unit, the working pressure of rectifying tower is at 0.1 ~ 2MPa, and temperature condition is at the bottom of tower 65 ~ 90 DEG C, tower top 35 ~ 50 DEG C.
The method of 20. olefinic polymerizations as claimed in claim 19, is characterized in that:
In described separating unit, the working pressure of rectifying tower is close with the pressure of the second reactor.
The method of 21. olefinic polymerizations as claimed in claim 17, is characterized in that:
The service temperature of the second reactor 80 ~ 85 DEG C, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio are the hydrogen of the 0.01 ~ 0.1, three reactor and polymerization single polymerization monomer mol ratio is 0.0001 ~ 0.001.
The method of 22. olefinic polymerizations as claimed in claim 17, is characterized in that:
The service temperature of the second reactor 70 ~ 75 DEG C, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio are the hydrogen of the 0, three reactor and polymerization single polymerization monomer mol ratio is 0.001 ~ 0.01.
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| US10173951B2 (en) * | 2016-09-13 | 2019-01-08 | Chevron Phillips Chemical Company Lp | Side rectifier column for olefin and diluent recovery |
| CN106957382B (en) * | 2017-04-11 | 2019-04-16 | 浙江大学 | A kind of method and apparatus of dynamic operation production polyolefin |
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| US11326004B2 (en) | 2017-10-14 | 2022-05-10 | Tpc Group Llc | Isobutylene copolymers, method for making isobutylene copolymers and isobutylene copolymer products |
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| KR20210016573A (en) * | 2018-05-30 | 2021-02-16 | 보레알리스 아게 | Method of making multimode high density polyethylene |
| CN112313252B (en) | 2018-05-31 | 2023-04-18 | Sabic环球技术有限责任公司 | Process for preparing multimodal polyolefins |
| CN112839965B (en) * | 2018-10-15 | 2023-06-20 | Sabic环球技术有限责任公司 | Process for preparing multimodal polyolefins |
| CN111748049B (en) * | 2019-03-27 | 2021-07-16 | 中国石油化工股份有限公司 | Olefin polymerization method and system |
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| CN114989340A (en) * | 2022-06-28 | 2022-09-02 | 杭州双安科技有限公司 | Olefin polymerization method |
| CN116023572A (en) * | 2022-11-21 | 2023-04-28 | 山东京博石油化工有限公司 | High-temperature solution polymerization process for copolymerization of ethylene and alpha-olefin |
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