CN103387628A - Alkene polymerization system and method - Google Patents
Alkene polymerization system and method Download PDFInfo
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Abstract
The invention provides an alkene polymerization system and method. The system comprises more than three reactors connected in series. The first reactor is one or more than two annular pipe reactors; the second reactor is one or more than two stirring kettle reactors; and the third reactor is one or more than two gas-phase fluidized-bed reactors. A catalyst and a reaction material enter a first reactor and is subjected to a polymerization reaction; the reaction product with the catalyst enters the second reactor, the material is supplemented into the second reactor, and a reaction is carried out; the product from the outlet of the second reactor enters the third reactor, the material is supplemented into the third reactor, and a reaction is carried out; and a final product is obtained in the third reactor. The system and method provided by the invention is used for producing ultra-wide-molecular-weight-distribution polyolefin with excellent mechanism performances and processing performances.
Description
Technical field
The present invention relates to a kind of high molecular polymerization field, 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 molecular weight and help the raising of the mechanical property of resin, but also can make the processing of resin become difficult simultaneously.And broad peak (sometimes also referred to as bimodal or multimodal) polyolefin resin can be realized the balance of materials processing performance and mechanical property, low molecular weight part wherein can guarantee that resin has good processing characteristics, the mechanical property that the while high molecular is partly given material, as high tensile property, high tenacity and shock strength etc.The reactors in series combination process is to produce at present the most widely used industrial method with broad peak molecular weight distribution polyolefin resin, this method is under the reaction conditions that two or more gas with various forms, 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.For example CN101790544A and CN200580033634.6 mention carries out the combination process of olefinic polymerization at least in the slurry loop reactor of two series connection, and the method for bimodal polyethylene of producing in two slurry reaction stills of mentioning in CN1903896A.Above technique is all by light constituent and polymkeric substance in flasher or fractionation plant separation the first reactor outlet slurry.These class methods adopt slurry-phase reactor in the second reactor, the amount of comonomers that adds is subject to the restriction of reactor fouling, and can not the higher product of production co-monomer content, and this second reactor a kind of requirement of producing high molecular weight products just.Simultaneously, due to two kinds of reaction conditionss only can be provided, 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 of for example mentioning 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, be subjected to reaction product easily to stop up the impact of reactor and line of pipes, this type of reactor is not suitable for producing low-molecular-weight product, and the target product of this first reactor while producing just the broad peak distribution of products.
This area is the technique of known a kind of slurry-phase reactor+Gas-phase reactor also.The polyethylene multistage production technique of for example mentioning in EP0517868 and CN1708515A, wherein first paragraph is the slurry polymerization in annular-pipe reactor under super critical condition, second segment is to carry out vapour phase polymerization in one or more Gas-phase reactor.Need in this processing method the degree of the effluent flash distillation of the first reactor to " basically removing all residual solution ", thereby need a large amount of energy.In addition, do not mention in the method if reclaim efficiently " residual solution " that flashes off.
CN101400933A discloses and has a kind ofly carried out suspension polymerization in three reactors that are connected in series, and produces " multi-modal " polyethylene molding composition (being the polymkeric substance of a kind of multimodal or broad peak molecular weight distribution).This composition is comprised 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 anti-environmental stress disruptiveness and notched impact strength has had significant raising.But, because this patent in the end still adopts slurry reaction in first order reaction, with gas-phase reaction, compare, the material that the needs that reaction is carried secretly during discharging reclaim is more, separates and reclaims comparatively difficulty, big energy-consuming and need to increase investment.
CN101035851A has also mentioned a kind of preparation method of multimodal polyethylene composition, and this composition comprises three ethylene homo or copolymerization parts with different weight-average molecular weight.Its preferred implementation is to realize 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 and CN1708515A.
Therefore, need to find a kind of more economic and gentle polyolefin process that comprises three or three above reactors that is in series of reliable slurries, for the production of the product of super wide molecular weight distribution.
Summary of the invention
, for the problems of the prior art, the purpose of this invention is to provide a kind of system and method for olefinic polymerization.The system and method for this olefinic polymerization, can produce the polyolefine of super wide molecular weight distribution, and production cost is lower, flow process is more reasonable, more energy-conservation.
An object of the present invention is to provide a kind of system of olefinic polymerization, it comprises the reactor more than three that is connected in series.Wherein, the first reactor is one or more annular-pipe reactor; The second reactor is one or more stirred-tank reactor; The 3rd reactor is one or more gas-phase fluidized-bed reactor; Reaction mass enters the first reactor and carries out polyreaction, with the reaction product of 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 reaction obtains final product in the 3rd reactor finally.Above-mentioned reaction mass comprises catalyzer, thinner and reaction raw materials etc.; Supplement material, comprise the supplementary catalyzer of needs, thinner, reaction raw materials etc.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, reduce energy and material consumption, preferably at the second reactor, be outside equipped with separating unit; The 3rd reactor is outside equipped with knockout drum.Catalyzer and reaction mass enter the first reactor and carry out polyreaction, with the reaction product of catalyzer, enter the second reactor, supplement material and from the liquid phase of separating unit, add together the second reactor, 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 of separating and supplementary mixing of materials, enter the 3rd reactor, and reaction obtains final product in the 3rd reactor; The gas that evaporates in the second reactor enters separating unit, and here with the liquid phase discharging of gas-liquid separator, contact, isolate light, weigh two kinds of components, heavy constituent (containing thinner, comonomer) is with all or part of second reactor that returns of liquid form, and light constituent goes the aftertreatment recovery system with the gas phase form.
The second reactor in system of the present invention, be in stirred-tank reactor, can utilize the heat of the polyreaction generation that occurs in reactor, make in the first reactor effluent that enters reactor the light constituent flash separation and with polymer slurries, separate, thus realization response and the coupling that separates in a reactor.
Described separating unit can comprise one or two above rectifying tower, for separating of going out the second needed component of reactor and unwanted component, and the component that needs, namely according to keeping the required component of reactant concn, is returned to the second reactor in the desired amount.A kind of preferred version is to adopt at least one rectifying tower with 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 as required the second or the 3rd reactor, in the side line extraction, substantially do not contain 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, can control the amount of comonomers that enters the second reactor by the lateral line discharging amount like this, at the bottom of tower, discharging is mainly thinner, can loop back as required the second or first reactor, overhead extraction is rich in the light constituent of alkene and hydrogen, sees accompanying drawing 3.
By selecting rational separating unit, heavy constituent (containing thinner, comonomer) and light constituent are carried out necessary separating, make the operation between the second reactor and the 3rd reactor relatively independent.Simultaneously, control the amount that enters the comonomer in the second reactor, make the second reactor operate under required reactant concn, the final control that realizes the polyolefin products quality of producing in the second reactor.
So, compare with two gas-phase reactor processes of the use series connection of mentioning in EP-A-691353 and US4420592, due to adding of the second reactor and separating unit in system of the present invention, make the operational condition of each reactor relatively independent, avoided material between reactor that two gas-phase reactor processes run into to have the problem of altering mutually.Compare with the tandem process of annular-pipe reactor+Gas-phase reactor of mentioning in EP0517868 and CN1708515A, utilize the polyreaction heat release to make the light constituent evaporation, avoided using the high pressure flash method of high energy consumption to carry out the separation of light constituent, had good energy-saving effect.
In system of the present invention, the effluent of the second reactor (reaction product) keeps the state of its slurries directly to enter the 3rd reactor (gas-phase fluidized-bed reactor), the liquid evaporation that contains in effluent can be used for removing the reaction heat of the 3rd reactor, this is identical with the described what is called of patent CN1171793 " condensation process ", can improve the space-time yield of the 3rd reactor.
In addition, particularly, the reaction product slurry of described the 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; The compressed machine of gas-liquid separator separates gas phase out compresses and supplements mixing of materials, enters the 3rd reactor.
According to system of the present invention, second purpose of the present invention is to provide a kind of method of olefinic polymerization, and it comprises the following steps:
1) raw material that makes the polyreaction that comprises olefinic polymerization monomer, catalyzer in described the first reactor, polymerization under the condition that the first reactant concn exists, output is with the reaction product of catalyzer;
2) reaction product with catalyzer of above-mentioned the first reactor output enters described the second reactor; In the second reactor,, with the supplementary material that adds, form the second reactant concn, the reaction product of output the second reactor;
3) reaction product of above-mentioned the second reactor enters described the 3rd reactor,, with the polymerization under the condition of formed the third reactant concn of supplementary material, obtains polyolefin products.
Described formation reactant concn refers to pass in and out by adjustment the reaction product quantity of 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 the second reactor, isolates the gas that decompression process obtains, and gas enters separating unit; The reaction product that stays, with the supplementary material that adds, and form 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 the 3rd reactor, the circulation gas of the 3rd reactor outlet enters gas-liquid separator, the gas phase of separating and supplementary mixing of materials, enter the 3rd reactor, polymerization under the condition of formed the third reactant concn, obtain polyolefin products.
The reaction product of described the 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, enter the 3rd reactor.
The method of olefinic polymerization of the present invention, polymerization process condition in its each reactor, comprise temperature, pressure etc., reaction raw materials used (comprising polymerization single polymerization monomer, comonomer, hydrogen), thinner, catalyzer etc. and consumption etc., wait and all adopt olefinic polymerization polymerization process condition commonly used in prior art.
Specifically, polymerization single polymerization monomer described in olefine polymerizing process of the present invention is the monoolefine of C2～C4, and preferred C2, preferably include comonomer in the supplementary material in described the second reactor and the 3rd reactor, described comonomer is the alkene or derivatives thereof of C3～C8, preferred hexene-1.Wherein comonomer and the polymerization single polymerization monomer mol ratio in the second reactor is 0.001～1.Comonomer and polymerization single polymerization monomer mol ratio in the 3rd reactor are 0.001 ~ 0.2, are preferably 0.01～0.1, and greater than the comonomer in the second reactor and polymerization single polymerization monomer mol ratio.
The thinner that uses in the first reactor and the second reactor, be selected from least a in propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane, preferred Trimethylmethane.
In the method for the invention, at the 3rd reactor, carry out condensation or the solidifying operation of supercool,, to improve the space-time yield of reactor, increase the heat energy power of removing of reactor.The induced condensing agent of wherein introducing is unreactive hydrocarbons, and described unreactive hydrocarbons are selected from least a in Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane.In the 3rd reactor, be to remove heat problem in order to solve better polyreaction adding of induced condensing agent, and in the first reactor and the second reactor adding of thinner be the flowability problem that improves polymeric reaction product.If induced condensing agent and thinner adopt same substance, corresponding tripping device need not be set separate, can simplify process.Therefore, the preferred material identical with thinner in the first reactor of induced condensing agent.
Catalyzer in described the first reactor is selected from least a in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse;
Add or do not add catalyzer in described the second reactor and the 3rd reactor;
When adding catalyzer in the second reactor and the 3rd reactor, this catalyzer is selected from least a in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse.
The method of olefinic polymerization of the present invention, contain higher hydrogen in the first reactant concn in described the first reactor, and consequently the molecular weight of the first reactor effluent is lower; And at described the second reactor and the 3rd reactor, produce olefin copolymer respectively under the second reactant concn and the 3rd reactant concn condition.Wherein in the first reactor hydrogen/the polymerization single polymerization monomer mol ratio is 0.05 ~ 2, preferred 0.1 ~ 0.6; In the second reactor hydrogen/the polymerization single polymerization monomer mol ratio is 0 ~ 0.5, is preferably 0, namely do not add hydrogen; The hydrogen of the 3rd reactor/polymerization single polymerization monomer mol ratio is 0.0001 ~ 0.1, and preferred hydrogen less than the first reactor/polymerization single polymerization monomer mol ratio.
The service temperature of described the first reactor is 20 ~ 130 ℃, preferred 75 ~ 115 ℃; Working pressure is 0.1 ~ 10.0MPa, preferred 3.0 ~ 5.0MPa.The service temperature of described the second reactor is 60 ~ 95 ℃, preferred 70 ~ 85 ℃; Working pressure is 0.1 ~ 2.0MPa, preferred 0.7 ~ 1.6MPa.The service temperature of described the 3rd reactor is 60 ~ 130 ℃, preferred 70 ~ 110 ℃; Working pressure is 1.0 ~ 4.0MPa, preferred 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 ℃, 35 ~ 50 ℃ of tower tops.
One of preferred version of method of the present invention is to produce the low-molecular-weight polyolefine of high-density in the first reactor; Produce the polyolefine of low density high molecular 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 the post-treatment process with appropriate pars intermedia, and this series products is called the polyolefine of the super wide molecular weight distribution of the first kind.While adopting this preferred version, preferred 80 ~ 85 ℃ of the service temperature of the second reactor, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio be preferred the 0.01 ~ 0.1, the 3rd reactor hydrogen/the polymerization single polymerization monomer mol ratio is preferred 0.0001 ~ 0.001.
Another preferred version of method of the present invention is the low-molecular-weight polyolefine of production high-density in the first reactor; Produce the polyolefine of low density high molecular in the 3rd reactor; And in the second reactor the polyolefine of production ultra-high molecular weight, the product of gained is the super wide molecular weight distribution polyolefin of Equations of The Second Kind, its mechanical property particularly anti-environmental stress disruptiveness and notched impact strength has had significant raising.While adopting this preferred version, preferred 70 ~ 75 ℃ of the service temperature of the second reactor, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio for be preferably 0, the three reactor hydrogen/the polymerization single polymerization monomer mol ratio is preferred 0.001 ~ 0.01.
Above-mentioned preferred version is the polyolefine that how to prepare needed super wide molecular weight distribution in order to illustrate, but not limits the scope of the invention.
According to the present invention, more specifically olefinic polymerization flow process is as follows:
It is annular-pipe reactor that catalyzer and reaction mass (polymerization single polymerization monomer, hydrogen etc.) enter the first reactor, and carries out polyreaction therein.The reaction product slurry is after decompression and heat exchange, and entering the second reactor with the slurries of catalyzer is stirred-tank reactor.Containing the supplementary material of comonomer and the liquid phase discharging of separating unit also simultaneously adds the second reactor to react together.The gas that evaporates in the second reactor enters separating unit, and here with the liquid phase discharging of gas-liquid separator, contacts, and separates thinner, comonomer and light constituent.It is gas-phase fluidized-bed reactor that the outlet slurry of the second reactor enters the 3rd reactor.The circulation gas of the 3rd reactor outlet enters gas-liquid separator after heat exchange is cooling,, with supplementary mixing of materials, enter the 3rd reactor after the compressed pressurization of the gas phase of separating, and reaction obtains final product in the 3rd reactor.
Now a plurality of steps of the inventive method are described in detail:
A. the first reactor
Described the first reactor, namely in annular-pipe reactor, carry out the homopolymerization of olefinic polymerization monomer such 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 ℃, preferred 70 ~ 115 ℃, and more preferably 85 ~ 110 ℃; Working pressure is 0.1 ~ 10.0MPa, preferred 3.0 ~ 5.0MPa.Hydrogen/monomer mol ratio in reactor is 0.05 ~ 2, preferred 0.1 ~ 0.6.Selected catalyzer can be Ziegler-Natta catalyst, metallocene catalyst or the centers catalyse agent of Nonmetallocene monomer and their mixture.
Produce the low-molecular-weight polymkeric substance of high-density, 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 the first reactor effluent enters the second reactor through reducing valve and First Heat Exchanger, and namely stirred-tank reactor, carry out alkene such as ethene in inert hydrocarbon diluent, with the copolyreaction of comonomer such 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 ℃, preferred 70 ~ 85 ℃; Working pressure is 0.1 ~ 2.0MPa, preferred 0.7 ~ 1.6MPa.Select in reactor add or do not add hydrogen, hydrogen and polymerization single polymerization monomer mol ratio while adding hydrogen in reactor 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, perhaps no longer adds new catalyzer.
The heat that utilizes polyreaction to produce in the second reactor, make the light constituent flash distillation that enters reactor, realization separates with polymer slurries, thereby realization response and the coupling that separates in a reactor makes 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 a kind of preferred version is to produce " fused layer " part crucial between bimodal distribution, with appropriate pars intermedia, assigns to avoid high molecular or low molecular weight part " to separate out " in the post-treatment process.Also having a kind of preferred version is the polyolefine of production ultra-high molecular weight, significantly to improve polyolefinic processing characteristics and mechanical property.
C. the 3rd reactor
Described the second reactor effluent enters the 3rd reactor, i.e. gas-phase fluidized-bed reactor.The operational condition of this reactor is basic identical with conventional fluidized-bed reactor, approximately 60～130 ℃ of its operating temperature ranges, preferred 70 ~ 110 ℃; Working pressure scope 1.0 ~ 4.0MPa, preferred 1.5 ~ 2.5MPa.The hydrogen/monomer mol ratio of the 3rd reactor is 0.0001 ~ 0.1 and preferably less than the hydrogen/monomer mol ratio of the first reactor.Comonomer and polymerization single polymerization monomer mol ratio in the 3rd reactor are 0.001 ~ 0.2, and the mol ratio of preferred comonomers and polymerization single polymerization monomer is 0.01～0.1 and greater than the mol ratio of the comonomer 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, perhaps no longer adds new catalyzer.
Can use the solidifying operation of condensation or supercool in described the 3rd reactor,, to improve the space-time yield of reactor, increase the heat energy power of removing of reactor.The solidifying manipulation require of condensation or supercool is introduced one or more unreactive hydrocarbons, for example Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane and their mixture, the preferably material identical with thinner in the first reactor.
Produce the polymkeric substance of low density high molecular, its melting index MI in the 3rd reactor
21.6Below 50g/10min, density is at 935kg/m
3Below.The polyolefine of the super wide molecular weight distribution that generates finally is intermittently or continuous discharging by the 3rd reactor.
D. separating unit
Described separating unit can be one or more rectifying tower, and for separating of going out the second needed component of reactor and unwanted component, and the component that needs is returned to the second reactor.Relevant flow process is described below: the circulation gas of the 3rd reactor advanced the second interchanger and entered gas-liquid separator after cooling, the liquid phase discharging of gas-liquid separator contacts with the vaporised gas of the second reactor in separating unit, reclaim thinner such as Trimethylmethane in vaporised gas, separating unit liquid phase discharging recycle as required.
A kind of preferred version of separating unit is to use at least one rectifying tower with the side line extraction.The working pressure of tower can be at 0.1 ~ 2MPa, and is preferably close with the pressure of the second reactor.Preferred temperature condition is at the bottom of tower 65 ~ 90 ℃, 35 ~ 50 ℃ of tower tops.In actually operating, when comonomer is heavier than thinner, comonomer and thinner are gone out from tower bottom flow, loop back as required the second or the 3rd reactor, substantially do not contain the thinner of copolymerization component in the side line extraction, 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, can control the amount of comonomers that enters the second reactor by the lateral line discharging amount like this, at the bottom of tower, discharging is mainly thinner, can loop back as required the second or first reactor, overhead extraction is rich in the light constituent of alkene and hydrogen, sees accompanying drawing 3.
By regulating the separating power of separating unit, control the amount that enters the comonomer in the second reactor, make the operation between the second reactor and the 3rd reactor relatively independent, and can realize the control to the polyolefin products quality of producing in the second reactor.
Utilize method of the present invention, can produce the polyolefine of the super wide molecular weight distribution with very good mechanical properties and processing characteristics, particularly polyethylene.The polyolefine of so-called super wide molecular weight distribution, refer to that molecular weight distribution is wider than common bimodal polyolefin, and have some special part to strengthen polyolefinic processing characteristics and/or mechanical property.This area adopts polydispersity coefficient PDI to weigh the width that polyolefin molecular weight distributes 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 super wide molecular weight distribution of the present invention is higher than common bimodal polyolefin, and its molecular weight distribution, 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 characteristics and effect:
1., by controlling the reaction conditions of three reactors, produce the polyolefine of the super wide molecular weight distribution with very good mechanical properties and processing characteristics.The first reactor adopts slurry reaction, produces the lower product of molecular weight, and the 3rd reactor adopts gas-phase reaction, the convenient more product of comonomer of producing.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, with appropriate pars intermedia, assign to avoid high molecular or low molecular weight part to be separated in the post-treatment process; Also having a kind of preferred version is the polyolefine of production ultra-high molecular weight in the second reactor, significantly improves polyolefinic processing characteristics and mechanical property.
2. the second reactor in the present invention, stirred-tank reactor, the effect of light constituent in playing simultaneously polyreaction and separating the first reactor effluent, be the device of a kind of reaction and separation coupling, makes simultaneously the operation between the first reactor and the 3rd reactor relatively independent.The heat that utilizes polyreaction to produce in this reactor, make the light constituent flash distillation that enters reactor, and realization separates with polymer slurries, thus realization response and the coupling that separates in a reactor, the investment of having saved equipment.
3. by regulating the separating power of described separating unit, control enters the amount of the comonomer in the second reactor, make the operation between the second reactor and the 3rd reactor relatively independent, and can realize the control to the polyolefin products quality of producing in the second reactor.
4. can use the solidifying operation of condensation or supercool in described the 3rd reactor,, to improve the space-time yield of reactor, increase the heat energy power of removing of reactor.
Description of drawings
Fig. 1 olefin polymerization reaction unit schematic diagram of the present invention.
Fig. 2 separating unit of the present invention is selected an olefin polymerization reaction unit schematic diagram with side line extraction rectifying tower.Its lateral line discharging enters the first reactor.
Fig. 3 separating unit of the present invention is selected an olefin polymerization reaction unit schematic diagram with side line extraction rectifying tower.Its lateral line discharging enters the 3rd reactor.
Description of reference numerals:
1 first reactor 2 reducing valve 3 First Heat Exchangers
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 in order to further illustrate the present invention, but not limit the scope of the invention.
Olefinic polyreaction flow process as shown in Figure 1 is as follows: the reaction mass that contains catalyzer enters the first reactor 1, annular-pipe reactor, and carry out therein polyreaction.The reaction product slurry after reducing valve 2 and First Heat Exchanger 3, enters the second reactor 4, stirred-tank reactor with the slurries of catalyzer.Containing the supplementary material of monomer and the liquid phase discharging of separating unit 10 rectifying tower also simultaneously adds the second reactor 4 to react together.In the second reactor 4, the gas of evaporation enters separating unit 10, and here with the liquid phase discharging of gas-liquid separator 8, contacts, and separates thinner, comonomer and light constituent.The outlet slurry of the second reactor 4 enters the 3rd reactor 6, gas-phase fluidized-bed reactor.The circulation gas of the 3rd reactor 6 outlets enters gas-liquid separator 8 after the second interchanger 7 is cooling,, with the mixing of materials of supplementing, enter the 3rd reactor 6, and reaction obtains final product in the 3rd reactor 6 after compressed machine 9 pressurizations of the gas phase of separating.
Embodiment 1
As shown in Figure 1, produce the polyethylene of super wide molecular weight distribution in the reactor of three series connection, output is 300,000 ton/years, 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, 95 ℃ of temperature of reaction, pressure 4.0MPa together.The inlet amount of therein ethylene is 19962kg/hr, regulates the hydrogen feed amount, and making the hydrogen/ethylene molar ratio in slurries is 0.234.In reactor effluent, poly output is 18750kg/hr, and in slurries, the shared massfraction of polymkeric substance is 45%.
After the annular-pipe reactor effluent advanced decompression, its temperature became 65 ℃, and pressure is 1.25MPa, and contained 35.5% gas phase composition, then entered the second reactor 4---stirred-tank reactor.The temperature of reaction of this reactor is 75 ℃, and pressure is 1.06MPa.The reactor fresh feed only contains ethene, flow is 2554kg/hr, and by separating unit 10, control and enter the thinner Trimethylmethane of reactor and the amount of comonomer hexene-1, making hexene-1/ ethylene molar ratio in gas phase in reactor is 0.244, hydrogen/ethylene molar ratio is 0.106.In reactor effluent, poly flow is 20625kg/hr, and in slurries, the shared massfraction of polymkeric substance is 34%.
The stirred-tank reactor effluent enters the 3rd reactor 6---and continue polymerization in gas-phase fluidized-bed reactor, temperature of reaction is 92 ℃, 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 the super wide molecular distribution of the described first kind, 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 a rectifying tower with lateral line discharging as separating unit.At this moment, the rectifying tower lateral line discharging enters the first reactor; Go the inventory (being 25363kg/hr after optimizing) of aftertreatment recovery system from separating unit 10, and add the diluent mass flow (being 20710kg/hr after optimizing) of the first reactor 1 can reduce respectively 1300kg/hr.And the operational condition of each reactor is constant, therefore can obtain the finished product of same quality and quantity.
It is identical with embodiment 1 that the operational condition of the first reactor 1 and the 3rd reactor 6 and material form selection, and by regulating the separating power of middle separating unit 10, control the second reactor 4---the operational condition of stirred-tank reactor, realize producing the poly purpose of the super wide molecular distribution of Equations of The Second Kind.
The temperature of reaction of the second reactor is 75 ℃, and pressure is 1.6MPa.Do not add comonomer in reactor, fresh feed only contains ethene, and flow is 1098kg/hr, is controlled the amount of the thinner Trimethylmethane that enters reactor by separating unit 10, to guarantee normally carrying out of slurry reaction.Hydrogen/ethylene molar ratio in reactor is 0.106.In reactor effluent, poly flow is 20625kg/hr, and in slurries, the shared massfraction of polymkeric substance is 43%.
Reactor effluent is the polyethylene of the super wide molecular distribution of described Equations of The Second Kind, 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 Examples
Comparative Examples is to produce polyethylene in the double loop reactor of series connection.In described flow process, Ziegler-Natta catalyst and thinner Trimethylmethane, and ethene, hydrogen enter the first ring pipe reactor, 96 ℃ of temperature of reaction, pressure 4.2MPa together.The inlet amount of therein ethylene is 17620kg/hr, regulates the hydrogen feed amount, and making the hydrogen/ethylene molar ratio in slurries is 0.58.In reactor effluent, poly output is 17273kg/hr, and in slurries, the shared massfraction of polymkeric substance is 46%.
First ring pipe reactor effluent advanced reduction vaporization remove the light constituents such as hydrogen after, enter the second annular-pipe reactor.Temperature of reaction is 84 ℃, and pressure is 3.0MPa.Control feed composition, making the hydrogen/ethylene molar ratio in slurries is 0.00669, and hexene-1/ ethylene molar ratio in reactor is 1.13.In reactor effluent, poly flow is 35961kg/hr, and in slurries, the shared massfraction of 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 (20)
1. the system of an olefinic polymerization, comprise the reactor more than three that is connected in series, and it is characterized in that:
The first reactor is one or more annular-pipe reactor; The second reactor is one or more stirred-tank reactor; The 3rd reactor is one or more gas-phase fluidized-bed reactor;
Reaction mass enters the first reactor and carries out polyreaction, with the reaction product of 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 reaction obtains final product in the 3rd reactor finally.
2. the system of olefinic polymerization as claimed in claim 1 is characterized in that:
Described the second reactor is outside equipped with separating unit; Described the 3rd reactor is outside equipped with knockout drum;
The circulation gas of described the 3rd reactor outlet enters gas-liquid separator, and the gas phase of separating and supplementary mixing of materials, enter the 3rd reactor; The liquid phase of separating is all or part of enters described separating unit; The gas that evaporates in the second reactor enters separating unit, and here with the liquid phase discharging of gas-liquid separator, contact, isolate light, weigh two kinds of components, heavy constituent is with all or part of second reactor that returns of liquid form, light constituent goes the aftertreatment recovery system with the gas phase form.
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 with lateral line discharging, and its lateral line discharging enters the first reactor or the 3rd reactor.
5., as the system of the described olefinic polymerization of any one of claim 2 ~ 4, it is characterized in that:
The reaction product of described the 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; The compressed machine of gas-liquid separator separates gas phase out compresses and supplements mixing of materials, enters the 3rd reactor.
6. an employing, as the method for the olefinic polymerization of system as described in any one of claim 1 ~ 5, is characterized in that comprising the following steps:
1) raw material that makes the polyreaction that comprises olefinic polymerization monomer, catalyzer in described the first reactor, polymerization under the condition that the first reactant concn exists, output is with the reaction product of catalyzer;
2) reaction product with catalyzer of above-mentioned the first reactor output enters described the second reactor; In the second reactor,, with the supplementary material that adds, form the second reactant concn, the reaction product of output the second reactor;
3) reaction product of above-mentioned the second reactor enters described the 3rd reactor,, with the polymerization under the condition of formed the third reactant concn of supplementary material, obtains polyolefin products.
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 the second reactor, isolates the gas that decompression process obtains, and gas enters separating unit; The reaction product that stays, with the supplementary material that adds, and form 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 the 3rd reactor, the circulation gas of the 3rd reactor outlet enters gas-liquid separator, the gas phase of separating and supplementary mixing of materials, enter the 3rd reactor, polymerization under the condition of formed the third 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 the 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, enter the 3rd reactor.
9., as the method for the described olefinic polymerization of any one of claim 6 ~ 8, it is characterized in that:
Described polymerization single polymerization monomer is the monoolefine of C2～C4;
Include comonomer in supplementary material in described the second reactor and the 3rd reactor, described comonomer is the alkene or derivatives thereof of C3～C8;
Comonomer in wherein said the second reactor and the mol ratio of polymerization single polymerization monomer are 0.001～1;
Comonomer in described the 3rd 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 the C2 monoolefine;
Comonomer in described the second reactor and the 3rd reactor is hexene-1;
Comonomer in described the 3rd reactor and the mol ratio of polymerization single polymerization monomer are 0.01～0.1 and greater than the mol ratio of the comonomer in the second reactor and polymerization single polymerization monomer.
11. the method for olefinic polymerization as claimed in claim 9 is characterized in that:
In reactant in described the first reactor, hydrogen and polymerization single polymerization monomer mol ratio are 0.05 ~ 2;
In reactant in described the second reactor, hydrogen and polymerization single polymerization monomer mol ratio are 0 ~ 0.5;
In reactant in described the 3rd reactor, hydrogen and polymerization single polymerization monomer mol ratio are 0.0001 ~ 0.1.
12. the method for olefinic polymerization as claimed in claim 11 is characterized in that:
Hydrogen and polymerization single polymerization monomer mol ratio in described the first reactor are 0.1 ~ 0.6;
Do not add hydrogen in described the second reactor;
Hydrogen in described the 3rd reactor and polymerization single polymerization monomer mol ratio are less than the hydrogen in the first reactor and polymerization single polymerization monomer mol ratio.
13. the method for olefinic polymerization as claimed in claim 9 is characterized in that:
The thinner that uses in the first reactor and the second reactor is selected from least a in propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane.
14. the method for olefinic polymerization as claimed in claim 9 is characterized in that:
Described the 3rd reactor carries out the solidifying operation of condensation or supercool, and the induced condensing agent of wherein introducing is unreactive hydrocarbons, and described unreactive hydrocarbons are selected from least a in Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene, hexane, heptane; The preferred material identical with thinner in the first reactor.
15. the method for olefinic polymerization as claimed in claim 9 is characterized in that:
Catalyzer in described the first reactor is selected from least a in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse;
Add or do not add catalyzer in described the second reactor and the 3rd reactor;
When adding catalyzer in the second reactor and the 3rd reactor, this catalyzer is selected from least a in Ziegler-Natta catalyst, metallocene catalyst, the agent of Nonmetallocene monomer centers catalyse.
16. the method for olefinic polymerization as claimed in claim 9 is characterized in that:
The service temperature of described the first reactor is 20 ~ 130 ℃; Working pressure is 0.1 ~ 10.0MPa;
The service temperature of described the second reactor is 60 ~ 95 ℃; Working pressure is 0.1 ~ 2.0MPa;
The service temperature of described the 3rd reactor is 60 ~ 130 ℃; Working pressure is 1.0 ~ 4.0MPa.
17. the method for olefinic polymerization as claimed in claim 16 is characterized in that:
The service temperature of described the first reactor is 75 ~ 115 ℃; Working pressure is 3.0 ~ 5.0MPa;
The service temperature of described the second reactor is 70 ~ 85 ℃; Working pressure is 0.7 ~ 1.6MPa;
The service temperature of described the 3rd reactor is 70 ~ 110 ℃; Working pressure is 1.0 ~ 2.5MPa.
18. the method for olefinic polymerization as claimed in claim 16 is characterized in that:
In 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 ℃, 35 ~ 50 ℃ of tower tops.
19. the method for olefinic polymerization as claimed in claim 16 is characterized in that:
80 ~ 85 ℃ of the service temperatures of the second reactor, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio are that hydrogen and the polymerization single polymerization monomer mol ratio of the 0.01 ~ 0.1, the 3rd reactor is 0.0001 ~ 0.001.
20. the method for olefinic polymerization as claimed in claim 16 is characterized in that:
70 ~ 75 ℃ of the service temperatures of the second reactor, working pressure is 0.7 ~ 1.6MPa; Hydrogen and polymerization single polymerization monomer mol ratio are that hydrogen and the polymerization single polymerization monomer mol ratio of 0, the three reactor is 0.001 ~ 0.01.
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