CN1203925A - Process for propylene polymerization - Google Patents
Process for propylene polymerization Download PDFInfo
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- CN1203925A CN1203925A CN 98115164 CN98115164A CN1203925A CN 1203925 A CN1203925 A CN 1203925A CN 98115164 CN98115164 CN 98115164 CN 98115164 A CN98115164 A CN 98115164A CN 1203925 A CN1203925 A CN 1203925A
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Abstract
The invention discloses a process for propylene polymerization comprising the steps of feeding propylene containing not less than 0.1 % by weight and not more than 20 % by weight of propane to a polymerization reactor, distilling at least a part of unreacted propylene discharged from the reactor to remove propane contained in the unreacted propylene, and circulating the purified propylene into the polymerization reactor, whereby propane is drawn out from the polymerization reaction system. The propane concentration in the unreacted propylene discharged from the polymerization reactor is in the range of usually 90 to 98 % by weight, and the purified propylene concentration to be circulated into the reactor after the distillation can be set in the range of 60 to 98 % by weight. At least a part of the purified propylene obtained after the distillation is preferably circulated into the reactor as a liquid.
Description
The present invention relates to the method for propylene polymerization, from polymerization reactor, remove effectively in this method as the propane of impurity with polypropylene effectively.The present invention relates to the propene polymerizing method that heat of polymerization wherein also can be used effectively more specifically.
In olefinic polymerization, the raw material that polymerization is used is through joining in the polymerization reaction system behind the purifying in advance.In the purge process of polymer raw, not only removing usually has dysgenic impurity to polyreaction, but also removes the polyreaction inertia and do not influence the impurity of resulting polymers product quality.
Especially be used as under the situation of polymer raw at propylene, polyreaction inert propane is included in the impurity.That is to say that propylene comprises the propane as impurity usually, and in general comprise the propane of about 5% (weight) in the technical grade propylene.
In propylene polymerization processes, the common recirculation of the unreacting propylene of discharging from polymerization reactor is to carry out polyreaction, this is undertaken by unreacting propylene is recycled in the polymerization reactor with liquid form (obtaining by the cooling unreacting propylene) or with gas form, and this has nothing to do with vapour phase polymerization or liquid polymerization.
In the process recycling of unreacting propylene, in fact circulation contains the unreacting propylene of propane.Propane is inert for polyreaction, can in polyreaction, not be consumed, therefore can accumulation with the propane of together introducing as the propylene (raw material propylene) of raw material in the polymerization reactor along with the carrying out of polyreaction, thereby make the propane concentration in the polymerization reactor rise, the response capacity of propylene (efficient) descends relatively.
In order to prevent above problem, as mentioned above, propylene joins in the polymerization reactor after normally therefrom removing propane again.
Yet, in the process of from propylene, removing propane, be difficult to, because propylene and propane have lower boiling (being respectively-47.0 ℃ and-42.1 ℃) under barometric point by simple water distilling apparatus separating propane from propylene.For this reason, the distillation purifying of propylene is generally conducted at an elevated pressure, but the boiling-point difference between propylene and propane becomes more little more along with the increase of distillation pressure, so that reflux ratio must become is big.This just needs large-sized water distilling apparatus, and makes energy expenditure huge.And large-sized high pressure distillation device is very expensive.So the cost height of purifying propylene, thereby polyacrylic production cost has also improved.
The present invention makes in these cases, the method that the purpose of this invention is to provide a kind of propylene polymerization, it can use undersized water distilling apparatus that propane is separated from propylene, reduces energy expenditure, and removes propane effectively with polypropylene effectively from polymerization reaction system.
Propene polymerizing method of the present invention is a kind of like this method, and it comprises the limit polypropylene, the unreacting propylene that discharge from polymerization reactor to the polymerization reactor internal recycle on the limit, wherein:
Contain the propylene that is no less than 0.1% (weight) and no more than 20% (weight) propane and be added in the polymerization reactor as the polyreaction raw material,
Distillation at least a portion unreacting propylene of discharging from polymerization reactor to be removing propane contained in the unreacting propylene, and the propylene of purifying like this is recycled in the polymerization reactor, removed propane thus from polymerization reaction system.
In aforesaid method, be preferably from polymerization reactor and discharge and the propane content of desire by the unreacting propylene of distillation purifying is generally 0.1 to 60% (weight), be 100% (weight) in the propylene and the propane total amount of from polymerization reactor, discharging.
The propane concentration that hope is removed by distillation is 100% (weight) in the propane removed by distillation and the total amount of propylene in the scope of 90 to 98% (weight).
Wish that distillation back round-robin density of propylene in polymerization reactor is 100% (weight) to come out to be recycled into the propane in the polymerization reactor and the total amount of propylene from water distilling apparatus in the scope of 60 to 98% (weight).
Remove propane and the propylene of purifying by circulation by distillation, can the controlled polymerization reactor in the concentration (or concentration of propane) of propylene, thereby can change the pressure of polyreaction.
Desiring to be recycled into purified propylene in the polymerization reactor after the distillation, to be preferably at least a portion be liquid.
In the present invention, control desires to be recycled into the gas-liquid percentage (gas-liquid fractions) (amount of liquefied propylene) of the purified propylene in the polymerization reactor and the amount of the unreacting propylene of discharging from reactor as mentioned above, thus the polymeric reaction temperature in can the controlled polymerization reactor.
If the inventive method is undertaken by These characteristics, can from polymerization reaction system, remove propane effectively so, and polypropylene effectively.
Fig. 1 is the synoptic diagram of an embodiment of the liquid polymerization of propene polymerizing method of the present invention.
Fig. 2 is the synoptic diagram of an embodiment of the vapour phase polymerization of propene polymerizing method of the present invention.
Below describe propene polymerizing method of the present invention in detail.
The implication of term used herein " polymerization " is not limited to " homopolymerization ", also comprises " copolymerization ". Equally, originally The used term " polymer " of literary composition " implication be not limited to " homopolymers ", also comprise " copolymer ".
Propene polymerizing method of the present invention is so a kind of method, and it comprises the limit polypropylene, the limit unreacting propylene that circulation is discharged from polymer reactor in the polymer reactor, wherein:
Contain the propylene that is no less than 0.1% (weight) and no more than 20% (weight) propane and be added in the polymer reactor as the polymerisation raw material,
The unreacting propylene that distillation at least a portion is discharged from polymer reactor is contained to remove in the unreacting propylene Propane, the propylene of purifying like this is recycled in the polymer reactor, from polymerization reaction system, removed thus Propane.
The propylene that is used as the propylene polymerization Raw contains sometimes has dysgenic impurity to polymerisation, Such as water, carbon monoxide, carbon dioxide and alcohol. Before propylene was added into polymer reactor, these were to polymerization Reaction has dysgenic impurity sometimes by adsorption treatment or adopt as required other processing to remove.
Yet raw material propylene contains quite a large amount of impurity to the polymerisation inertia, such as propane. In order to improve The efficient of distillation, the Cmin that needs propane is 0.1% (weight), is 0.5% (weight) preferably, better Be 5% (weight), the total amount of propylene and propane is as 100% (weight) in the raw material propylene. In order to improve polymerization The efficient of reaction, the maximum concentration that needs propane are 20% (weight), are 10% (weight) preferably, with raw material The total amount of propylene and propane is 100% (weight) meter in the propylene.
As mentioned above, separating propane must be undertaken by distillation from propylene. In the present invention, anti-to polymerization Should have dysgenic impurity to remove by absorption or other method, but propane is not basically from raw material propylene The middle removal, the propylene that will contain propane joins in the polymer reactor.
In the present invention, propylene polymerization can be poly-with liquid phase polymerization (slurry polymerization or homogeneous solution polymerization) or gas phase Incompatible carrying out.
In addition, propylene can homogeneous polymerization, perhaps can with other monomer copolymerization of the following stated. Need to not add Enter to remove the propane as impurity contained in these monomers before other copolymerisable monomer, just with the situation of propylene The same.
In reaction system, as the hydrogen of molecular weight regulator, to the varsol of polymerisation inertia (such as oneself Alkane) or inert gas (such as nitrogen) but can with the monomer coexistence of propylene and other copolymerization.
Though the kind of the required performance of propene polymer, copolymerisable monomer and the type of copolymerization ratio and polyreaction are depended in the variation of polymerizing condition, the pressure of polyreaction usually at barometric point to 100kg/cm
2Scope in, be that barometric point is to 50kg/cm preferably
2Scope in, polymeric reaction temperature is in 20 to 200 ℃ scope, preferably in 40 to 150 ℃ scope.Polyreaction can two step or more step carry out.
The molecular weight of gained propene polymer can be regulated by the consumption of control hydrogen (molecular weight regulator), perhaps regulates by changing polymerizing condition (as polymeric reaction temperature).
Describe the method for propylene polymerization in detail below in conjunction with accompanying drawing.
Fig. 1 is the synoptic diagram of an embodiment of propene polymerizing method of the present invention, and this embodiment is carried out with liquid polymerization method.
As mentioned above, to polymerization reactor 1, add propane content for being no less than the raw material propylene (usually with liquid form) of 0.1% (weight) and no more than 20% (weight) from raw material pipeline 1a.
In polymerization reactor 1, in the presence of the following catalyzer that adds from catalyzer pipeline 1b, propylene polymerization in liquid phase (perhaps with the copolymerisable monomer copolymerization that adds from for example raw material pipeline 1a).If desired, can to polymerization reactor 1, add varsol (as hexane) from optional reinforced pipeline (not shown).
The polymeric solution of discharging from polymerization reactor 1 contains propene polymer and unreacting propylene.This polymeric solution is incorporated into the separator 3 (as flash drum or funnel) by heat exchanger 2 from pipeline 1c.In separator 3, polymeric solution is separated into propene polymer and unreacting propylene.Reclaim propene polymer by pipeline 3b then.
On the other hand, unreacting propylene is recycled into the polymerization reactor 1 by compressor 4 from the circulation line 3a of separator 3, and this unreacting propylene contains the propane of together introducing with raw material.This unreacting propylene can contain hydrogen, copolymerisable monomer and catalyst component.
In the present invention, before the circulation unreacting propylene enters polymerization reactor 1, from least a portion unreacting propylene, remove propane by distillation.Particularly, at least a portion unreacting propylene among the circulation line 3a is introduced in the water distilling apparatus 5 by pipeline 5a, and is separated into propylene and propane by distillation.
The amount that is introduced into the unreacting propylene the water distilling apparatus 5 from circulation line 3a depends on the propane concentration in the polymerization reactor.Unreacting propylene among the circulation line 3a can partly or entirely be introduced in the water distilling apparatus 5.In general, the unreacting propylene of hope in will the circulation line 3a of about 50-100% (weight) introduced in the water distilling apparatus 5.
The above-mentioned propane of separating by water distilling apparatus 5 is discharged from outside the reaction system from pipeline 5c.
On the other hand, purified propylene cools off by heat exchanger 6, enters the polymerization reactor 1 from pipeline 5b circulation then.Be preferably before purified propylene circulation enters polymerization reactor 1, the purified propylene of at least a portion is liquefied.
Fig. 2 is the synoptic diagram of an embodiment of propene polymerizing method of the present invention, and it carries out with gas phase polymerization process.
As Fig. 1, identical raw material propylene adds the polymerization reactor 11 from raw material pipeline 11a.
In polymerization reactor 11, propylene is at vapour phase polymerization (perhaps with other monomer copolymerization).If desired, can in polymerization reactor 11, add rare gas element (as nitrogen).
The propene polymer of gained is discharged from polymer recovery outlet 11c continuously or off and on.
The unreacting propylene of discharging from the pipeline 11d of polymerization reactor 11 contains the propane of together introducing with raw material.This unreacting propylene can contain hydrogen, copolymerisable monomer, rare gas element and catalyst component.This unreacting propylene cools off with heat exchanger 12 usually, uses separator (gas-liquid separator) 13 to be separated into phlegma and gas phase then.14 circulations enter polymerization reactor 11 to gas phase through compressor from pipeline 13a, and phlegma enters polymerization reactor 11 from pipeline 13b circulation.
In the present invention, at least a portion phlegma (unreacting propylene) among pipeline 13b 5a by the road is introduced into water distilling apparatus 5, becomes propylene and propane by fractionation by distillation.That is to say that the same with the situation of Fig. 1, unreacting propylene is through distillation purifying, propane is discharged from outside the reaction system, and purified propylene circulation enters in the polymerization reactor 11.The amount of introducing the unreacting propylene (phlegma) of water distilling apparatus 5 from circulation line 13b depends on the propane concentration the polymerization reactor 11, and the unreacting propylene among the circulation line 13b can partly or entirely also be introduced in the water distilling apparatus 5.In general, wish in water distilling apparatus 5, to introduce the unreacting propylene of the about 50-100% (weight) among the circulation line 13b.
The propane of separating by water distilling apparatus 5 is discharged from outside the reaction system from pipeline 5c as mentioned above.
On the other hand, purified propylene is cooled by heat exchanger 6, and circulation enters polymerization reactor 11 through pipeline 5b then.Be preferably before purified propylene circulation enters polymerization reactor 11, the purified propylene of at least a portion is liquefied.
Process with propane fractionation by distillation from unreacting propylene is below described among Fig. 1 and Fig. 2 in more detail in water distilling apparatus 5.
Propane fractionation by distillation from unreacting propylene can be carried out when polyreaction causes, perhaps can after polyreaction enters steady state, carry out.High propane concentration in the unreacting propylene can obtain high distillation efficiency.Therefore in the present invention, from the distillation efficiency angle, be preferably when the propane concentration in the propane in the reaction system accumulation and the unreacting propylene of discharging from polymerization reactor reaches and begin to distill after a certain amount of, although can be after polyreaction causes, just begin immediately to distill during the propane concentration when the propane concentration in the reaction system is lower than the steady state of polyreaction.Can make in the reactor propane concentration method that equates with the propane concentration of polyreaction steady state that becomes after polyreaction causes, begin immediately to distill by before polyreaction causes, introducing propane.
If necessary, can change distillation rate (distillation rate) after reaching steady state, to continue distillation.Perhaps according to circumstances will distill the total reflux state that temporarily remains on.
In the present invention, wishing that distillation propane content is 0.1 to 60% (weight), is 5 to 60% (weight) preferably, better is 10 to 50% (weight), and good again is the unreacting propylene of 10 to 40% (weight).This propane concentration is the value in propylene in the unreacting propylene of 100% (weight) and propane total amount, is the propane concentration in the polymerization reactor 1 basically.
Usually low pressure or highly compressed fractional column known to can be used as water distilling apparatus 5.The unreacting propylene that contains high density propane in the present invention distills by above-mentioned, and fractional column only need include the structure that reclaims plate (recovery zone), can also carry dense plate (enriching section) if desired.The distillation purifying of unreacting propylene can carry out under hitherto known condition.
In the present invention, the polymer raw of therefrom not removing propane is added in the polymerization reactor, so propane has high density in the polymerization reactor.If distillation contains the unreacting propylene of high density propane, propane can be distilled from unreacting propylene effectively to be removed, thereby the size of water distilling apparatus can diminish.
That is to say that compare with the situation of distillation purifying raw material propylene, not only carrying dense plate in the present invention only need randomly provide, and the number of recovery plate can reduce significantly also.And, can make that the size of water distilling apparatus is quite little, can make that reflux ratio is little.The result can reduce the energy expenditure that is used to remove propane.
Wish to discharge propane concentration outside the reaction system in 90 to 98% (weight) from pipeline 5c, preferably in the scope of 94 to 98% (weight), being that 100% (weight) is condition from the propane of pipeline 5c discharge and the total amount of propylene by above-mentioned distillation.
Hope circulates through water distilling apparatus 5 purifying, from pipeline 5b and enters the density of propylene of polymerization reactor in 60 to 98% (weight), preferably in the scope of 70 to 95% (weight), be that 100% (weight) is condition with the propylene that comes out to circulate to enter polymerization reactor from water distilling apparatus 5 and the total amount of propane.
By making the circulation of purified propylene enter polymerization reactor as mentioned above, the density of propylene in the may command polymerization reactor (or propane concentration), thus can change the pressure of polyreaction.
In addition, by the control desire from the amount of pipeline 5b round-robin liquefied propylene, i.e. the gas-liquid percentage of propylene, and the amount of the unreacting propylene of from polymerization reactor, discharging by control, the polymeric reaction temperature in just can the controlled polymerization reactor.
(synoptic diagram of liquid-phase polymerization and gas phase polymerization embodiment is described) below in conjunction with the accompanying drawings propene polymerizing method of the present invention has been described, but the invention is not restricted to these accompanying drawings.
In propylene polymerization of the present invention, propylene can with other monomer copolymerization.Other monomeric example comprises the alpha-olefin that contains 2 to 18 carbon atoms, as ethene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene; The cyclenes that contains 3 to 18 carbon atoms; By CR
2The vinylidene aromatic monomer that=CR-Ph represents (respectively do for oneself hydrogen or methyl, Ph of each R is the phenyl that phenyl or contraposition alkyl replace, and R and Ph can have halogenic substituent) is as vinylbenzene; Vinyl monomer is as vinylchlorid, vinyl acetate, vinyl acrylate, methyl methacrylate, tetrafluoroethylene, vinyl ether and vinyl cyanide; Conjugated diolefine is as divinyl and isoprene; Unconjugated polyene, as 1,4-hexadiene, dicyclopentadiene and 5-vinyl-2-norbornylene; The alkynes class is as acetylene and propine; And aldehydes, as formaldehyde.
But two or more are used in combination these monomers.
The equal useful as catalysts of propylene polymerization catalyzer of any routine and without particular limitation is as metallocene catalyst, Ziegler-type titanium catalyst and Philips (Philip) type chromium oxide catalyst.
Catalyst for polymerization of propylene generally includes transition metal catalyst component and cocatalyst component, also comprises electron donor(ED) preferably.
The used transition metal catalyst component of the present invention is the transistion metal compound [A] that is selected from periodictable IV B family, and this transistion metal compound is represented by for example following formula (ⅰ):
MLx (ⅰ)
Wherein, M is the transition metal that is selected among Zr, Ti, Hf, V, Nb, Ta and the Cr; L is and the ligand of transition-metal coordination, is hydrogen atom, halogen atom, Sauerstoffatom, substituent alkyl, alkoxyl group, aryloxy, trialkylsilkl (trialkylsilyl group) or the SO that contains 1 to 30 carbon atom can be arranged
3R group (R is the alkyl that contains 1 to 8 carbon atom, and it can contain substituting group (as halogen)); X is the valency of transition metal.
The example of halogen atom comprises fluorine, chlorine, bromine and iodine.
The example that contains the alkyl of 1 to 30 carbon atom comprises:
Alkyl is as methyl, ethyl, propyl group, sec.-propyl and butyl;
Cycloalkyl is as cyclopentyl and cyclohexyl;
Aryl is as phenyl, tolyl and cyclopentadienyl;
Aralkyl, as benzyl and neophyl (2-methyl-2-phenyl propyl) (neophyl).
Cycloalkyl, aryl and aralkyl can partly be replaced by halogen atom, alkyl and trialkylsilkl.
During a plurality of alkyl coordination in being selected from cycloalkyl, aryl and aralkyl, the silylene that they can be by alkylidene group (as ethylidene and propylidene), the alkylidene group (as isopropylidene and diphenylmethylene), silylene and the replacement that replace (silica-based as dimethylated methylene, phenylbenzene silylene and aminomethyl phenyl silylene) comes bonding.
The example of alkoxyl group comprises methoxyl group, oxyethyl group and butoxy.Examples of aryloxy comprises phenoxy group.
Above-mentioned compound can two or more be used in combination, and they can use with hydrocarbon or halohydrocarbon dilution back.
Transistion metal compound can add in the polymerization system by solid form.For example, transistion metal compound can contact with the bead-type substrate compound, together uses with carrier compound.The example of carrier compound comprises mineral compound, as SiO
2, A1
2O
3, B
2O
3, MgO, ZrO
2, CaO, TiO
2, ZnO, Zn
2O, SnO
2, BaO, MgCl
2And NaCl; And resin, as polyethylene, polypropylene, poly-1-butylene, poly(4-methyl-1-pentene) and vinylbenzene/divinyl benzene copolymer.Carrier can two or more be used in combination.Carrier compound can form particle with the transistion metal compound contact phase time.
Solid-state transition metal catalyst component can be the solid titanium catalyst component that comprises magnesium, titanium, halogen and electron donor(ED), and it can obtain by for example magnesium compound, titanium compound and electron donor(ED) being contacted with each other.
The cocatalyst component that can be used to form olefin polymerization catalyst is the compound that is selected from [B] organo-aluminium compound, halogenation organo-aluminium compound, aluminum halide compounds, organoboron compound, organic boron-oxygen, halogenation organoboron compound, halogenation boron compound and the Organoaluminoxy compound (organoaluminum oxy-compound).
Compound except that the Organoaluminoxy compound [B] is represented with following formula (ⅱ):
BRx (ⅱ)
Wherein B is aluminium atom or boron atom.
When the compound shown in the formula (ⅱ) was organo-aluminium compound or organoboron compound, R represented to contain the alkyl of 1 to 30 carbon atom.
When the compound shown in the formula (ⅱ) was aluminum halide compounds or halogenation boron compound, R represented halogen atom.
When the compound shown in the formula (ⅱ) was halogenation organo-aluminium compound or halogenation organoboron compound, R represented to contain the alkyl and the halogen atom of 1 to 30 carbon atom.
The example of halogen atom comprises fluorine, chlorine, bromine and iodine.The example that contains the alkyl of 1 to 30 carbon atom comprises methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-.
The Organoaluminoxy compound is represented with following formula (ⅲ) or (ⅳ):
In following formula, R is an alkyl, and as methyl, ethyl, propyl group or butyl, m is 2 or bigger integer, is preferably 5 to 40 integer.
Aikyiaiurnirsoxan beta (Organoaluminoxy compound) can be formed by blended aluminum alkoxide unit, and these aluminum alkoxide unit are by using chemical formula OAl (R
1) (R
1Be the group identical with above R) the aluminum alkoxide unit of expression and with chemical formula OAl (R
2) (R
2Be the group identical with above R, but and R
1Difference) the aluminum alkoxide unit of expression is formed.
A plurality of R part in the aluminum alkoxide unit can respectively do for oneself halogen, hydrogen, alkoxyl group, aryloxy or hydroxyl.
The used Organoaluminoxy compound of the present invention can be the benzene-insoluble Organoaluminoxy compound described in the Japanese patent application publication No. No.78687/1990.
Cocatalyst component [B] can two or more be used in combination.They can use with hydrocarbon or halohydrocarbon dilution back.
In the present invention, electron donor(ED) can be used as the component of propylene polymerization catalyzer with transition metal catalyst component and cocatalyst component.The example of electron donor(ED) comprises ether compound, carbonyl compound and alkoxy compound.
In addition, can use the catalyzer of pre-polymerization in the present invention, it forms by making alkene prepolymerization on above-mentioned catalyst component.
According to propene polymerizing method of the present invention, can from polymerization reaction system, remove propane effectively, thus polypropylene effectively.In the present invention, can make that the size of the water distilling apparatus that is used to remove propane is quite little, reflux ratio is diminished.Therefore, can reduce and remove the required energy expenditure of propane.
Claims (7)
1. the method for a propylene polymerization comprises the limit polypropylene, the unreacting propylene that discharge from polymerization reactor to the polymerization reactor internal recycle on the limit, wherein:
Contain the propylene that is no less than 0.1% (weight) and no more than 20% (weight) propane and be added in the polymerization reactor as the polyreaction raw material,
Distillation at least a portion unreacting propylene of discharging from polymerization reactor to be removing propane contained in the unreacting propylene, and the propylene of purifying like this is recycled in the polymerization reactor, removed propane thus from polymerization reaction system.
2. the method for propylene polymerization as claimed in claim 1, wherein discharging from polymerization reactor and the propane content of desire by the unreacting propylene of distillation purifying is 0.1 to 60% (weight), is 100% (weight) in propylene in the unreacting propylene and propane total amount.
3. the method for propylene polymerization as claimed in claim 1, wherein the concentration of the propane of removing by distillation is 100% (weight) in the propane removed by distillation and the total amount of propylene in the scope of 90 to 98% (weight).
4. the method for propylene polymerization as claimed in claim 1, the concentration that wherein is recycled into the propylene in the polymerization reactor after distillation is in the scope of 60 to 98% (weight), to enter the propane of polymerization reactor from water distilling apparatus circulation and the total amount of propylene is 100% (weight).
5. the method for propylene polymerization as claimed in claim 1, wherein will be by removing propane by distillation the propylene of purifying be recycled in the polymerization reactor concentration with propylene in the controlled polymerization reactor.
6. the method for propylene polymerization as claimed in claim 1 wherein will be distilled the propylene cooling that back desire circulation enters polymerization reactor, with liquefaction at least a portion propylene.
7. the method for propylene polymerization as claimed in claim 6, wherein the amount of the unreacting propylene of discharging from polymerization reactor by control and control use the gas-liquid percentage of the propylene that obtains as method as described in the claim 6 to come polymeric reaction temperature in the controlled polymerization reactor.
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|---|---|---|---|
| CN 98115164 CN1203925A (en) | 1997-06-26 | 1998-06-26 | Process for propylene polymerization |
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|---|---|---|---|
| JP170716/97 | 1997-06-26 | ||
| CN 98115164 CN1203925A (en) | 1997-06-26 | 1998-06-26 | Process for propylene polymerization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101547941B (en) * | 2006-12-28 | 2011-12-28 | 三菱化学株式会社 | Process for production of alpha-olefin low polymers |
-
1998
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101547941B (en) * | 2006-12-28 | 2011-12-28 | 三菱化学株式会社 | Process for production of alpha-olefin low polymers |
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