CN109456430A - A kind of liquid phase method polypropylene manufacturing process and its application - Google Patents
A kind of liquid phase method polypropylene manufacturing process and its application Download PDFInfo
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- CN109456430A CN109456430A CN201710795832.0A CN201710795832A CN109456430A CN 109456430 A CN109456430 A CN 109456430A CN 201710795832 A CN201710795832 A CN 201710795832A CN 109456430 A CN109456430 A CN 109456430A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to a kind of liquid phase method polypropylene manufacturing process comprising: step A, by polypropylene catalyst and liquid propylene, the raw reaction of hybrid concurrency in pre-polymerization reactor, obtains propylene pre-polymer；Pre-polymerization material is divided into multiply logistics according to predetermined ratio in pre-polymerization material distributing system by step B, respectively enters the multiple series polymerizations reactors in downstream；The pre-polymerization material includes the active catalyst and liquid propene that propylene pre-polymer is had obtained in step A；Step C in liquid propylene medium, carries out the homopolymerization or copolyreaction of propylene, obtains polypropylene product in the multiple series polymerizations reactors in downstream；And optionally step D, the polypropylene product is continued to the homopolymerization or copolyreaction of propylene in the gas phase.
Description
Technical field
The invention belongs to olefin polymerization technology fields, and in particular to a kind of liquid phase method polypropylene manufacturing process and its application.
Background technique
As demand of the world to petroleum chemicals continues to increase, petrochemical plant and oil plant are expanded production repeatedly, by-product propylene
Scale is also increase accordingly.In this condition, each petrochemical plant carries out Revamping, or construction to polyacrylic process units one after another
New PP production line.
For polypropylene there are many production technology, the reactor that different production technologies is mainly manifested in use is different.Using liquid
When phase bulk propylene is as polymerisation medium, the Ziegler-Natta catalyst polymerization activity of propylene polymerization is high, and cooling is also opposite
It is easy, thus is current the most widely used polypropylene manufacturing process.The Spheripol technique of Basell company uses two
Concatenated annular reactor carries out homopolymerization and random copolymerization, also referred to as loop polypropylene technique, passes through other dense fluidized
Bed gas-phase reactor can carry out crushing-resistant copolymerization production.The Hypol technique of three well oiling companies uses stirred tank Liquid-phase reactor
The mode combined with gas-phase fluidized-bed reactor.Hypol polymarization method for prodcing polyacrylates is according to there are many differences of reactor used quantity
Form, such as: the double gas-phase reactor of Two Liquid Phases reaction kettle, Two Liquid Phases reaction kettle list gas-phase reactor, single double gas phases of liquid phase reactor kettle
Reactor, single liquid phase reactor kettle list gas-phase reactor.
Hypol technique uses interval pre-polymerization.The technique activates catalyst in the catalyst preparation stage, then with it is micro-
It measures propylene and carries out prepolymerization, pre-polymerization multiple is usually at 3 times or less.Since pre-polymerization multiple is low, the polymerization of Hypol process catalyst is living
Property is also not very high.Catalyst suspends in hexane during pre-polymerization, conveys prepolymer to still reaction with hexane after pre-polymerization
In device.Therefore, Hypol technique polypropylene plant will consume several hundred tons of hexanes every year, these hexanes are not only with high costs, but also
Final residual increases polyacrylic fugitive constituent in polypropylene, reduces polyacrylic quality.
Ziegler natta catalyst used in propylene polymerization in initial reaction stage there are a reaction peak, at this moment thermal discharge
Greatly, it reacts after peak and sharply weakens.The thermal discharge on polymerization reaction peak must be controlled in reaction kettle cooling during normal production
Below ability.This reaction peak is in the first annular-pipe reactor in loop technology polypropylene plant.First annular-pipe reactor
Middle response intensity is high, and heat release is violent；And react then very weak in the second annular-pipe reactor.Production at high load is mentioned in polypropylene plant
When, the case where axial-flow pump of the first annular-pipe reactor is easy to appear power swing, therefore also become the production line production capacity and mention
High bottleneck.This reaction peak is in the first liquid phase reactor kettle in Hypol technique polypropylene plant.Due to tank reactor
Relative surface area is small, and exchange capability of heat is poor, and the first liquid phase reactor kettle, which becomes, restricts the bottle that Hypol technique list production line production capacity improves
Neck.In 200,000 tons of annual output or more newly-built of PP production line, without the factory using Hypol technique polypropylene technology
?.
For built Hypol technique and loop technology polypropylene plant, due to upstream petrochemical iy produced propylene source
Increase, is also faced with urgent technical need and carries out capacity expansion revamping.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of liquid phase method polypropylene
Production method.Capacity expansion revamping is carried out to existing loop technology polypropylene plant using this method, polypropylene dress can be effectively improved
The yield set；Capacity expansion revamping is carried out to existing Hypol technique polypropylene plant using this method, effectively improves polypropylene plant
It can reduce the hexane consumption of device while yield and reduce polyacrylic fugitive constituent.
For this purpose, the present invention provides a kind of liquid phase method polypropylene manufacturing process comprising:
Step A, by polypropylene catalyst and liquid propylene, the raw reaction of hybrid concurrency in pre-polymerization reactor, obtains propylene
Prepolymer；
Pre-polymerization material is divided into multiply logistics according to predetermined ratio in pre-polymerization material distributing system, respectively enterd by step B
The multiple series polymerizations reactors in downstream；The pre-polymerization material includes the active catalytic that propylene pre-polymer is had obtained in step A
Agent and liquid propene；
Step C in liquid propylene medium, carries out the homopolymerization or total of propylene in the multiple series polymerizations reactors in downstream
Poly- reaction, obtains polypropylene product；And optionally
The polypropylene product is continued the homopolymerization or copolyreaction of propylene by step D in the gas phase；
Wherein, the pre-polymerization material distributing system includes equipped with feed inlet, at least one rinse mouth and at least two dischargings
The multi-path conversion valve set of mouth, the pre-polymerization material distributing system are electrically connected with the controller.
According to the method for the present invention, in step, the temperature of the reaction is -10 to 50 DEG C；The pressure of the reaction is 1-
8MPa。
According to the method for the present invention, the polymer reactor is selected from annular-pipe reactor and/or tank reactor.
According to the method for the present invention, the upstream of the rinse mouth is equipped with propylene liguid feed-line, and the pipeline and flushing
Mouth connection.
According to the method for the present invention, in the multi-path conversion valve set, the feed inlet is connected with pre-polymerization reactor, institute
Discharge port different from downstream polymer reactor connections respectively are stated, are not connected between the discharge port, the feed inlet and flushing
It is not connected between mouthful.
According to the method for the present invention, the feed inlet in the multi-path conversion valve set and rinse mouth exist from different discharge ports respectively
The control periodical of controller switches connection, is divided into 0.01-60 minutes between the period.
According to the method for the present invention, the multi-path conversion valve set includes at least one four-way valve.
According to the method for the present invention, when the multi-path conversion valve set includes two or more four-way valves, upstream
Any discharge port of four-way valve is connected to the feed inlet of downstream four-way valve.
According to the method for the present invention, the comonomer for copolyreaction being carried out with propylene is selected from ethylene and C4-C10Alpha-olefin in
It is one or more.
According to the method for the present invention, in step C, the temperature of the reaction is 50-100 DEG C；The pressure of the reaction is 1-
8MPa。
According to the method for the present invention, in step D, the temperature of the reaction carried out in the gas phase is 50-150 DEG C；In the gas phase
The pressure of the reaction of progress is 1-4MPa.
Detailed description of the invention
It is next with reference to the accompanying drawing that invention is further described in detail.
Fig. 1 be include a four way ball valve multi-path conversion valve set pre-polymerization material distributing system structural schematic diagram.
Fig. 2 be include that the structures of two kinds of connected states of four way ball valve in the multi-path conversion valve set an of four way ball valve is shown
It is intended to.
Fig. 3 is the flow chart that a kind of embodiment of polypropylene production is carried out using existing loop technology production line.
Fig. 4 is the flow chart that a kind of embodiment of polypropylene production is carried out using loop technology production line of the invention.
Fig. 5 is the process that another embodiment of polypropylene production is carried out using loop technology production line of the invention
Figure.
Fig. 6 is the flow chart that a kind of embodiment of polypropylene production is carried out using existing Hypol production line.
Fig. 7 is the flow chart that a kind of embodiment of polypropylene production is carried out using Hypol production line of the invention.
Fig. 8 is the process that another embodiment of polypropylene production is carried out using Hypol production line of the invention
Figure.
In above-mentioned attached drawing, unless otherwise indicated, identical component is indicated by identical appended drawing reference.Attached drawing is not according to reality
The ratio on border is drawn.
Specific embodiment
Below in conjunction with drawings and examples, the invention will be further described, these embodiments only serve it is illustrative,
It is not limited to application range of the invention.
In view of there are occur in the first Liquid-phase reactor in existing loop technology and Hypol technique polypropylene manufacturing process
Weak problem was reacted in reaction peak and second liquid phase reactor, and the first liquid phase is anti-in existing liquid phase PP Production Technology
Device is answered easily to form heat exchange bottleneck, the present inventor has carried out experimental study extensively and profoundly in polypropylene production technical field
And find, the propylene pre-polymer flowed out from prepolymerization reactor can be distributed as needed by using pre-polymerization material distributing system
To concatenated different polymer reactors, it is possible thereby to solve occur reaction peak and second liquid phase reaction in the first Liquid-phase reactor
The heat exchange bottleneck for reacting weak problem in device, while the first Liquid-phase reactor being overcome to be formed, effectively improves the production of production line
Ability.Method of the invention, which is applied to existing loop technology PP production line, only to be needed to install a set of pre-polymerization material distribution system
System；It only needs to build a set of bulk prepolymerisation device and a set of pre-polymerization material distributing system applied to Hypol technique PP production line,
Device capbility can be effectively increased, and is invested less.And polypropylene manufacturing process provided by the invention and existing Hypol technique
Polypropylene manufacturing process is compared, and the continuous Prepolymerizing process of liquid-phase bulk provided by the invention can effectively improve the activity of catalyst,
And it no longer needs using hexane, save the cost.The present invention is based on what above-mentioned discovery was made.
Therefore, liquid phase method polypropylene manufacturing process according to the present invention includes:
Step A, by polypropylene catalyst and liquid propylene, the raw reaction of hybrid concurrency in pre-polymerization reactor, obtains propylene
Prepolymer；
Pre-polymerization material is divided into multiply logistics according to predetermined ratio in pre-polymerization material distributing system, respectively enterd by step B
The multiple series polymerizations reactors in downstream；The pre-polymerization material includes the active catalytic that propylene pre-polymer is had obtained in step A
Agent and liquid propene；
Step C in liquid propylene medium, carries out the homopolymerization or total of propylene in the multiple series polymerizations reactors in downstream
Poly- reaction, obtains polypropylene product；And optionally
The polypropylene product is continued the homopolymerization or copolyreaction of propylene by step D in the gas phase.
Polypropylene of the present invention can be homopolypropylene, atactic copolymerized polypropene or impact copolymer polypropylene.For
The monomer being copolymerized with propylene can be ethylene and/or the alpha-olefin with 4-10 carbon atom, including such as: ethylene, 1- butylene, 1-
Amylene, 1- hexene, 4- methyl iso-amylene, 1- octene, 1- decene etc..
Polypropylene catalyst is not particularly limited in the present invention, and can be can make urging for propylene polymerization known to any one
Agent, such as metallocene compound catalyst or metallocene (Ziegler-Natta) catalyst.Common catalyst is tool
There is the ziegler natta catalyst of high stereoselective.It is equal greater than 95% propylene that the catalyst can prepare isotactic index
Polymers.
Ziegler natta catalyst of the present invention with high stereoselective can be various energy commonly used in the art
Enough catalyst of catalysis propylene progress isotactic polymerization.Generally, the metallocene with high stereoselective is urged
Agent contains: (1) the solid catalyst activity component of titaniferous, and main component is magnesium, titanium, halogen and internal electron donor；(2) have
Machine aluminium compound cocatalyst component；And the external electron donor component that (3) are optional.
The available this kind of specific example containing active solid catalyst component be disclosed in CN85100997,
CN98126383.6、CN98111780.5、CN98126385.2、CN93102795.0、CN00109216.2、
In CN99125566.6, CN99125567.4, CN02100900.7.The catalyst can be used directly, can also be passed through
It is added after pre- complexing and prepolymerization.
The organo-aluminum compound of cocatalyst component as catalyst is preferably alkyl aluminum compound, is more preferably selected from three
Alkyl aluminum (such as: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, trioctylaluminum), aluminium diethyl monochloride, one
At least one of chloro-di-isobutyl aluminum, one aluminium ethide of dichloro and ethyl aluminum dichloride.
With Ti/Al molar ratio computing, the solid catalyst activity component and organo-aluminum compound cocatalyst component of titaniferous it
Than that can be 1:25 to 1:1000.
External donor compound as optional catalyst component is preferably organo-silicon compound, general formula RnSi
(OR') 4-n, 0 n≤3 < in formula, wherein R and R' are identical or different, and be each independently selected from alkyl, naphthenic base, aryl and
Halogenated alkyl, R may be halogen or hydrogen atom.Specifically, the organo-silicon compound can be but be not limited only to: four methoxies
Base silane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyl
Dimethoxysilane, dimethyl diethoxysilane, methyl-t-butyldimethoxysilane, isopropyl methyl dimethoxy silicon
Alkane, two phenoxy group dimethoxysilanes, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane,
Vinyltrimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy
Base silane, second, isobutyl dimethoxy silane, 2- ethyl piperidine base -2- t-butyldimethoxysilane, (the fluoro- 2- of 1,1,1- tri-
Propyl) -2- ethyl piperidine base dimethoxysilane, (the fluoro- 2- propyl of 1,1,1- tri-)-methyl dimethoxysilane etc..
With Al/Si molar ratio computing, the ratio between the alkyl aluminum compound and the organo-silicon compound can be 3:1 to 100:
1。
Three kinds of components of the ziegler natta catalyst with high stereoselective can be added directly into prepolymerization
It, can also be by being complexed and then being added in pre-polymerization reactor in advance well known to industry in reactor.Prepolymerization is in liquid
It is carried out continuously under phase bulk conditions.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc..The temperature of prepolymerization
Degree is -10 to 50 DEG C, preferably 0-40 DEG C.The pressure of prepolymerization is 1-8MPa, preferably 1.2-5.5MPa.It is prepolymerized
Multiple can control at 0.5 to 1000 times, and preferred multiple is 5.0 to 500 times, and preferred multiple is 20 to 300 times.
Term " pressure " of the present invention refers to reactor gauge pressure.
Term " pre-polymerization multiple " of the present invention refers to the grams for the polymer that every gram of catalyst preparation obtains.
Term " pre-polymerization reactor " of the present invention be liquid-phase bulk pre-polymerization reactor, can be continuous stirred tank or
Annular-pipe reactor.Prepolymerization carries out in liquid propylene, and a certain amount of propane can be contained in propylene.
In the case where there is pre- complex reactor, catalyst, alkyl aluminum and electron donor carry out in pre- complex reactor
Pre-contact (pre- complexing) forms active catalyst afterwards.Active catalyst can be such that propylene polymerize, and the catalysis without being complexed in advance
Agent cannot make propylene that polymerization reaction occur.Active catalyst and unreacted alkyl aluminum and electron donor mixture enter catalyst
It is mixed in feeding device with propylene.Propylene enters pre-polymerization reactor after mixing with active catalyst and carries out prepolymerization.
In the case where no pre- complex reactor, catalyst and alkyl aluminum and electron donor in pre-polymerization reactor into
Row pre-contact (pre- complexing) forms active catalyst, and then carries out prepolymerization with the propylene in pre-polymerization reactor.
In pre-polymerization reactor, becomes after active catalyst contact propylene and be suspended in propylene, polypropylene quality not
Break increased solid, that is, propylene pre-polymer.Material containing prepolymer and liquid propylene monomer pre-polymerization reactor to
In main polymer reactor transmission process, if there is prepolymer is adhered to pipeline, on valve, the polypropylene on prepolymer constantly increases
It is more, the feed-line of prepolymer will be blocked.Once block prepolymer pipeline, entire polypropylene plant just interrupted catalyst into
Material, cannot remain in operation and produce polypropylene.Its treating method can only dismantle prepolymer feed-line, manual removal tamper.
Due to being suspended in the special nature of prepolymer in propylene, the inner surface of feed-line must be it is bright and clean, to prevent
Only adhere to prepolymer.The logistics of prepolymer must also be ensured that enough flowing velocities, prevent prepolymer from settling in liquid propene.
If the flow velocity of prepolymer is inadequate, the particle of prepolymer also will appear adhered to one another, and block prepolymer pipeline.If taking ability
Conventional regulating valve controls and distributes prepolymer logistics in domain, and regulating valve and pipeline will block quickly.Therefore this field
Multiple reactor polymarization method for prodcing polyacrylates all uses the form of tandem reactor.
The present invention provides a kind of liquid phase noumenal method Propylene polymerization production technologies, change this field long-term existence polyolefin
Production will use the concatenated viewpoint of multiple reactor, also different from by multiple reactor contents import a reactor or container and
Connection mode.
Present invention employs a kind of pre-polymerization material distributing system of creativeness, which can will include propylene pre-polymerization
The catalyst of object and the pre-polymerization material of liquid propene monomer are divided into multiply logistics according to predetermined ratio, respectively enter the multiple of downstream
Main polymer reactor.The distribution system can guarantee that the logistics of pre-polymerization material has enough flowing velocities, and not have in system
Dead angle.Therefore, which is less likely to occur to block, it is ensured that operating steady in a long-term.
In above-mentioned liquid phase method polypropylene manufacturing process, the pre-polymerization material distributing system includes being equipped with feed inlet, at least one
The multi-path conversion valve set of a rinse mouth and at least two discharge ports, the pre-polymerization material distributing system are electrically connected with the controller.
The pre-polymerization material distributing system is sequence control system, and effect is to flow to specific reaction by the control of multi-path conversion valve set
The length of time of device flows to the pre-polymerization logistics capacity of the reactor to control.
In certain embodiments of the present invention, the sequence control system is located at the DCS (decentralised control of polypropylene plant
System) in.Preferably, pass through DCS control system transmission telecommunications number to live solenoid valve, solenoid valve control compressed air-driven institute
It states valve group and switches over movement.The multi-path conversion valve set is under the regulation of sequence control system, by pre-polymerization material by predetermined
Ratio is transported in the different main polymer reactor in downstream.
Heretofore described term " upstream " and " downstream " are with the flow direction of material for reference.
In above-mentioned liquid phase method polypropylene manufacturing process, the upstream of the rinse mouth is equipped with propylene liguid feed-line, and institute
Pipeline is stated to be connected to rinse mouth.The rinse mouth that the present invention is connected to by setting with propylene liguid feed-line, can be continually fed into
Appropriate propylene liguid, is rinsed device and pipeline, guarantees not deposit dead angle in device, keeps the prepolymer material being previously passed through residual
It is remaining to be not easy to deposit, to be not easy to plug equipment installation, guarantee operating steady in a long-term.
In above-mentioned liquid phase method polypropylene manufacturing process, in the multi-path conversion valve set, the feed inlet and prepolymerization
Reactor is connected, and the discharge port is connected to downstream difference polymer reactor, is not connected between the discharge port, the feed inlet
It is not connected between rinse mouth, the feed inlet and rinse mouth are connected to from different discharge ports respectively.
In above-mentioned liquid phase method polypropylene manufacturing process, feed inlet and rinse mouth in the multi-path conversion valve set respectively with
The periodically switching connection under the control of the controller of different discharge ports, is divided into 0.01-60 minutes, preferably 1- between the period
20 minutes, more preferably 2-10 minutes.
In above-mentioned liquid phase method polypropylene manufacturing process, the multi-path conversion valve set is by being selected from triple valve, four-way valve or six
One or more of port valve is composed, and the preferably described multi-path conversion valve set includes at least one four-way valve, preferably described
Four-way valve is four way ball valve.
In above-mentioned liquid phase method polypropylene manufacturing process, when the multi-path conversion valve set includes two or more four
When port valve, any discharge port of upstream four-way valve is connected to the feed inlet of downstream four-way valve.By being used in series multiple four-way valves,
The multiple series polymerizations reactors in downstream can be made to share a pre-polymerization reactor.
In certain embodiments of the present invention, the function of the pre-polymerization material distributing system is by multi-path switching valve
The pre-polymerization material flowed out from a pre-polymerization reactor is assigned in two reactors by group.Fig. 1 is the distribution of this pre-polymerization material
The schematic diagram of system.The distribution system include a four way ball valve 103, the four way ball valve include a prepolymer feed inlet 1,
One propylene rinse mouth 2 and the discharge port 3 being connected to respectively with the second polymer reactor 202 and with the first polymer reactor 201 connect
Logical discharge port 4, and be connected to prepolymer feed inlet 1 pipeline 1012, be connected to propylene rinse mouth 2 pipeline 1022, with
The pipeline 1031 of first polymer reactor 201 connection, the pipeline 1032 being connected to the second polymer reactor 202.The four way ball valve
It is remotely controlled by DCS control system.Typical control program is DCS control system transmission telecommunications number to live solenoid valve, electric
Magnet valve control compressed air-driven four way ball valve switches over movement.
Fig. 2 (a) and Fig. 2 (b) show two kinds of working conditions of four way ball valve in pre-polymerization material distributing system shown in Fig. 1.
In Fig. 2 (a) and Fig. 2 (b) four mouths of four way ball valve be respectively prepolymer feed inlet 1, propylene rinse mouth 2, polymerize with second it is anti-
The discharge port 3 and 4 for answering device 202 or the first polymer reactor 201 to be connected to.In the state of Fig. 2 (a), prepolymer stream is by pre-polymerization
Material feed inlet 1 enters four way ball valve 103, polymerize from the output of discharge port 3 being connected to the second polymer reactor 202 to second anti-
Device 202 is answered, propylene liguid enters four way ball valve 103 from propylene rinse mouth 2, from the discharging being connected to the first polymer reactor 201
4 output of mouth is rinsed pipeline with propylene to the first polymer reactor 201.In the state of Fig. 2 (b), prepolymer stream by
Prepolymer feed inlet 1 enters four way ball valve 103, polymerize from the output of discharge port 4 being connected to the first polymer reactor 201 to first
Reactor 201, propylene liguid enter four way ball valve 103 from propylene rinse mouth 2, go out from what is be connected to the second polymer reactor 202
Material mouth 3 is exported to the second polymer reactor 202, is rinsed to pipeline with propylene.Prepolymer feed inlet 1 and propylene rinse mouth 2
Always it is not connected to, the discharge port 3 being connected to the second polymer reactor 202 and the discharge port 4 being connected to the first polymer reactor 201
Always it is not connected to.Into the low temperature propylene of flushing the propylene preferable temperature and pre-polymerization reactor temperature close of rinse mouth 2.Due to
The pipeline for the prepolymer stream that do not circulate is in propylene always and rinses state, so that pre-polymerization material distributing system of the invention is not easy
It blocks.
In the state of normal operation, four way ball valve is controlled pre-polymerization material distributing system of the invention in DCS control system
Under the control of program in the state of Fig. 2 (a) (hereinafter referred to as A condition, pre-polymerization material lead to the second polymer reactor 202) and Fig. 2
(b) (hereinafter referred to as B state, pre-polymerization material lead to the first polymer reactor 201) period switches in the state of.The switching of four way ball valve
Period is known as time T, includes the time T of A condition in a complete switching cycleA, the time T of B stateB.When switching cycle
Between T usually at 0.01-60 minutes, preferably 1-20 minutes, it is 2-10 minutes more preferable.
In above-mentioned liquid phase method polypropylene manufacturing process, set from the difference of multi-path conversion valve set by the controller
The output speed of the prepolymer material of material mouth output.When the discharge port quantity of actual use is n, periodically between switching connection
It is divided into T, the feed rate of total prepolymer material is set as V, is set to from the time of the prepolymer material of different discharge port outputs
T1、T2、···、Tn, it is clear that T1+T2+···+Tn=T, then from the prepolymer feed rate V of different discharge port outputs1、
V2、···、VnIt is respectively as follows:
V1=V × T1/ T, V2=V × T2/ T, Vn=V × Tn/T。
The method provided through the invention may be implemented to individually adjust the prepolymer material speed from different discharge port outputs
Rate, to achieve the purpose that adjust polymerization reaction throughput rate.
In other embodiments of the invention, by introducing second four way ball valve, and second four way ball valve
Feed inlet be connected to the discharge port of first four way ball valve, the multi-path conversion valve set including two four way ball valves can be formed
Pre-polymerization material distributing system.The pre-polymerization material distributing system of multi-path conversion valve set including two four way ball valves may be implemented
The pre-polymerization material flowed out from a pre-polymerization reactor is assigned in three polymer reactors.
After pre-polymerization material distributing system, it is each concatenated poly- that active catalyst and propylene with prepolymer enter downstream
It closes reactor and carries out liquid phase polymerization.The polymer reactor be annular-pipe reactor or tank reactor, or both arbitrarily take
With combination.The temperature of the liquid-phase polymerization is 50-100 DEG C, preferably 60-95 DEG C；The pressure of reaction is 1-8MPa, preferably
For 1.2-5.5MPa；The time of reaction is 10-180 minutes, preferably 20-120 minutes.
After completing above-mentioned liquid phase polymerization, in the presence of products therefrom, it can also be relayed in subsequent gas-phase reactor
It is continuous to carry out polymerization reaction.Gas-phase reactor can be horizontal type agitated bed reactor, vertical mixing bed reactor and fluidized-bed reaction
Device etc..In some embodiments of the invention, it is 50- that the temperature of the reaction carried out in the gas phase, which is the temperature of polymerization reaction,
150 DEG C, preferably 60-95 DEG C；The pressure of reaction is 1-4MPa, preferably 1.2-3.5MPa.
Embodiment
Comparative example 1
100000 tons/year of loop technology PP production line, using bicyclic pipe Liquid-phase reactor.Its flow chart such as Fig. 3 institute
Show.
The prepolymerization mode of propylene is continuous liquid-phase bulk prepolymerization.Pre-polymerization reactor 101 is annular-pipe reactor, is led to
Crossing axial-flow pump makes material high-speed movement and augmentation of heat transfer in reactor.Pass through low temperature liquid propylene feed and pre-polymerization reactor
Chilled water in collet withdraws from polymerization reaction heat.Propylene feed passes through pipeline 1001 respectively and enters propylene cooler 102, passes through pipe
Line 1002 enters the first polymer reactor 201, enters the second polymer reactor 202 by pipeline 1003.Wherein, low temperature liquid third
Alkene is the propylene that raw material propylene is cooled to 10 DEG C through subcooler 102.Polypropylene catalyst series pass through pipeline 1011 and come from
After the cold propylene of pipeline 1021 converges, into pre-polymerization reactor 101.Recirculated water in 101 collet of pre-polymerization reactor is
The mixed solution of ionized water and ethylene glycol controls the temperature of prepolymerization reactor in setting temperature after mixing through the chilled water with charging
Degree.20 DEG C of prepolymerization temperature, polymerization pressure 3.4MPa, the prepolymerization time 8 minutes, obtain propylene pre-polymer, pre-polymerization multiple
For 150 grams of polymer/gram catalyst.
The production of the PP production line progress homopolymer trade mark.70 DEG C of the polymerization temperature of first polymer reactor 201, polymerization
Pressure 3.4MPa, polymerization reaction time 60 minutes, slurry concentration 50wt%, produce load was 8 ton/hours；Second polymerization reaction
70 DEG C, polymerization pressure 3.4MPa of the polymerization temperature of device 202, polymerization reaction time 40 minutes, slurry concentration 50wt%, produce load
It is 4 ton/hours.Obtained solid polymer and a large amount of unreacted propylene monomer mixture material, deaerating by flash lines 203 will
Propylene monomer recycling, solid polymer is washed, it is dry after carry out granulation packaging, finally obtain homo-polypropylene product.Polypropylene
The produce load of production line is 12 ton/hours.
Embodiment 1
100000 tons/year of loop technology PP production line, using bicyclic pipe Liquid-phase reactor, process is in comparative example 1
Existing PP Production Technology process on the basis of increase pre-polymerization material distributing system.In addition, as needed to second
The propylene feed of endless tube, the recirculated water of cooling carry out necessary transformation.Its flow chart is as shown in Figure 4.
The prepolymerization mode of propylene is continuous liquid-phase bulk prepolymerization.Pre-polymerization reactor 101 is annular-pipe reactor, is led to
Crossing axial-flow pump makes material high-speed movement and augmentation of heat transfer in reactor.Pass through low temperature liquid propylene feed and pre-polymerization reactor
Chilled water in collet withdraws from polymerization reaction heat.Propylene feed passes through pipeline 1001 respectively and enters propylene cooler 102, passes through pipe
Line 1002 enters the first polymer reactor 201, enters the second polymer reactor 202 by pipeline 1003.Wherein, low temperature liquid third
Alkene is the propylene that raw material propylene is cooled to 10 DEG C through subcooler 102, is then divided into two strands, and the propylene through pipeline 1021 is gone to pre-
Polymer reactor 101, the propylene through propylene liguid feed-line 1022 go to pre-polymerization material distributing system.Polypropylene catalyst body
It is after the cold propylene of pipeline 1011 and pipeline 1021 converges, into pre-polymerization reactor 101.Pre-polymerization reactor 101 presss from both sides
Recirculated water in set is the mixed solution of deionized water and ethylene glycol, controls prepolymerization reactor after mixing through the chilled water with charging
Temperature in set temperature.20 DEG C of prepolymerization temperature, the prepolymerization time 8 minutes, it is pre- to obtain propylene by polymerization pressure 3.4MPa
Polymers, pre-polymerization multiple are 150 grams of polymer/gram catalyst.
Prepolymerization product and unreacted propylene liguid are discharged by pre-polymerization reactor 101, distribute system into pre-polymerization material
System.Fig. 1 is the schematic diagram of this pre-polymerization material distributing system.The distribution system includes multi-path conversion valve set, by one four
Pass ball valve 103 forms.Pre-polymerization material enters four way ball valve 103 from prepolymer feed inlet 1 through pipeline 1012.Propylene liguid is through liquid
Propylene feed-line 1022 enters four way ball valve 103 from rinse mouth 2.Discharge port 3 is through pipeline 1032 and the second polymer reactor 202
Connection, discharge port 4 are connected to through pipeline 1031 with the first polymer reactor 201.Multi-path is remotely controlled by DCS control system to turn
Valve group is changed, so that pre-polymerization material enters four way ball valve 103 through prepolymer feed inlet 1, enters the second polymerization reaction by discharge port 3
Device 202 (shown in such as Fig. 2 (a)), propylene liguid enter four way ball valve 103 through rinse mouth 2 and enter the first polymerization reaction to discharge port 4
The pipeline 1031 of device 201 rinses；Or pre-polymerization material is made to enter four way ball valve 103 through prepolymer feed inlet 1, by discharge port 4
Into the first polymer reactor 201 (shown in such as Fig. 2 (b)), propylene liguid enters four way ball valve 103 to discharge port 3 through rinse mouth 2
Pipeline 1032 into the second polymer reactor 202 rinses.The four way ball valve is remotely controlled by DCS control system.Pass through journey
The switching cycle time T for setting four way ball valve of sequence software is 6 minute, the wherein time T of A conditionABe 2 minutes, B state when
Between TBIt is 4 minutes.
By pre-polymerization material distributing system, pre-polymerization material is divided into two streams according to 2:1 ratio, respectively enters subsequent string
The first polymer reactor 201 and the second polymer reactor 202 of connection.
The production of the PP production line progress homopolymer trade mark.70 DEG C of the polymerization temperature of first polymer reactor 201, polymerization
Pressure 3.4MPa, polymerization reaction time 60 minutes, slurry concentration 50wt%, produce load was 8 ton/hours.First polymerization reaction
Device 201 is connected by connecting pipeline 2011 with the second polymer reactor 202.70 DEG C of the polymerization temperature of second polymer reactor 202,
Polymerization pressure 3.4MPa, polymerization reaction time 40 minutes, slurry concentration 50wt%, produce load was 8 ton/hours.What is obtained consolidates
Body polymer and a large amount of unreacted propylene monomer mixture material, deaerate by flash lines 203 and recycle propylene monomer, solid is poly-
Close object it is washed, it is dry after carry out granulation packaging, finally obtain homo-polypropylene product.The produce load of PP production line is 16
Ton/hour, the produce load than the existing method in comparative example 1 improves 33%.
Embodiment 2
100000 tons/year of loop technology PP production line, using bicyclic pipe Liquid-phase reactor and single gas-phase reactor,
Process increases pre-polymerization material distributing system on the basis of existing PP Production Technology process.In addition, right as needed
The propylene feed of second endless tube, the recirculated water of cooling carry out necessary transformation.Its flow chart is as shown in Figure 5.
The prepolymerization mode and operating condition of propylene are same as Example 1.
Prepolymerization product and unreacted propylene liguid are discharged by pre-polymerization reactor, into pre-polymerization material distributing system.
Fig. 1 is the schematic diagram of this pre-polymerization material distributing system.The distribution system includes multi-path conversion valve set, by a four-way ball
Valve 103 forms.Pre-polymerization material enters four way ball valve 103 from prepolymer feed inlet 1 through pipeline 1012.Propylene liguid is through propylene liguid
Feed-line 1022 enters four way ball valve 103 from rinse mouth 2.Discharge port 3 connects through pipeline 1032 and the second polymer reactor 202
Logical, discharge port 4 is connected to through pipeline 1031 with the first polymer reactor 201.Multi-path conversion is remotely controlled by DCS control system
Valve group enters the second polymer reactor by discharge port 3 so that pre-polymerization material enters four way ball valve 103 through prepolymer feed inlet 1
202 (shown in such as Fig. 2 (a)), propylene liguid enter four way ball valve 103 through rinse mouth 2 and enter the first polymer reactor to discharge port 4
201 pipeline 1031 rinses；Or make pre-polymerization material through prepolymer feed inlet 1 enter four way ball valve 103, by discharge port 4 into
Enter the first polymer reactor 201 (shown in such as Fig. 2 (b)), propylene liguid through rinse mouth 2 enter four way ball valve 103 to discharge port 3 into
The pipeline 1032 for entering the second polymer reactor 202 rinses.The four way ball valve is remotely controlled by DCS control system.Pass through program
The switching cycle time T for setting four way ball valve of software is 6 minute, the wherein time T of A conditionAIt is 2 minutes, the time of B state
TBIt is 4 minutes.
By pre-polymerization material distributing system, pre-polymerization material is divided into two streams according to 2:1 ratio, respectively enters downstream string
The first polymer reactor 201 and the second polymer reactor 202 of connection.
The production of the PP production line progress crushing-resistant copolymerization trade mark.70 DEG C of the polymerization temperature of first polymer reactor 201 gathers
Resultant pressure 3.4MPa, polymerization reaction time 60 minutes, slurry concentration 50wt%, produce load was 6 ton/hours.First polymerization is anti-
Device 201 is answered to connect by connecting pipeline 2011 with the second polymer reactor 202.The polymerization temperature 70 of second polymer reactor 202
DEG C, polymerization pressure 3.4MPa, polymerization reaction time 40 minutes, slurry concentration 50wt%, produce load was 6 ton/hours.It obtains
Solid polymer and a large amount of unreacted propylene monomer mixture material, through flash lines 203 and 204 flash liberation of flash tank by propylene
MONOMER RECOVERY.Solid polymer enters gas-phase reactor 205 and is copolymerized, and 75 DEG C of polymerization temperature, polymerization pressure 1.4MPa, polymerization
Reaction time 20 minutes, produce load was 3 ton/hours.Solid polymer is washed, it is dry after carry out granulation packaging, it is final
To homo-polypropylene product.The produce load of PP production line is 15 ton/hours, than existing double loop reactor list gas phase reaction
The operation productivity of device production line is obviously improved.
Comparative example 2
100000 tons/year of Hypol technique PP production line, using the double gas-phase reactor of Two Liquid Phases reaction kettle.Its process
Figure is as shown in Figure 6.
The prepolymerization mode of propylene is batch pre-polymerization.Catalyst suspends in hexane during prepolymerized, pre-polymerization times
Number is 3 times, after prepolymerization with hexane conveying prepolymer into tank reactor.
The production of the PP production line progress homopolymer trade mark.Main polymerized unit technological parameter are as follows: the first polymer reactor
The homopolymerization of 201 progress liquid phases, 70 DEG C of polymerization temperature, polymerization pressure 3.0MPa, polymerization reaction time 40 minutes, produce load 4
Ton/hour；Second polymer reactor 202 equally carries out the homopolymerization of liquid phase, 67 DEG C of polymerization temperature, polymerization pressure 2.7MPa, polymerize
Reaction time 40 minutes, produce load was 2 ton/hours.Obtained solid polymer and a large amount of unreacted propylene monomer mixing
Material after removing short-circuit catalyst and fine powder into powder scrubbing tower 203, carries out homopolymerization into the first gas-phase reactor 204
With the evaporation cooling of propylene liguid, 80 DEG C of polymerization temperature, polymerization pressure 1.7MPa, polymerization reaction time 70 minutes, produce load
It is 4 ton/hours；Solid polymer powder goes successively to the second gas-phase reactor 205 and carries out homopolymerization, 70 DEG C of polymerization temperature, polymerize
Pressure 1.5MPa, polymerization reaction time 60 minutes, produce load was 2 ton/hours.Obtained polymer powders are separated through circulating air
Device carries out gas solid separation, unreacted propylene monomer recycling, and solid polymer is washed, carries out granulation packaging after drying, most
Homopolypropylene product is obtained eventually.The produce load of PP production line is 12 ton/hours.
Embodiment 3
100000 tons/year of Hypol technique PP production line, using the double gas-phase reactor of Two Liquid Phases reaction kettle, process
Liquid-phase bulk prepolymerization device and pre-polymerization material are increased on the basis of the existing PP Production Technology process of comparative example 2
Distribution system.In addition, necessary transformation is carried out to the recirculated water of the propylene feed of second liquid phase reaction kettle, cooling as needed,
Necessary change is carried out to the propylene feed of the first gas-phase reactor and the second gas-phase reactor, the recirculated water of cooling as needed
It makes.Its flow chart is as shown in Figure 7.
The prepolymerization mode of propylene is continuous liquid-phase bulk prepolymerization.Pre-polymerization reactor 101 is that vertical stirred tank is anti-
Device is answered, so that material in kettle is uniformly mixed simultaneously augmentation of heat transfer using the oblique paddle stirrer of multilayer.By low temperature liquid propylene feed and
Chilled water in 101 collet of pre-polymerization reactor withdraws from polymerization reaction heat.Wherein, low temperature liquid propylene is raw material propylene through being subcooled
But device 102 is cooled to 5 DEG C of propylene, is then divided into two strands, and the propylene through pipeline 1021 goes to pre-polymerization reactor 101, through liquid
The propylene of state propylene feed-line 1022 goes to pre-polymerization material distributing system.Polypropylene catalyst series are by pipeline 1011 and pipe
After the cold propylene of line 1021 converges, into pre-polymerization reactor 101.Recirculated water in 101 collet of pre-polymerization reactor be from
The mixed solution of sub- water and ethylene glycol, temperature is -5 DEG C after ice maker is cooling.10 DEG C of prepolymerization temperature, polymerization pressure 3.4MPa,
The prepolymerization time 10 minutes, propylene pre-polymer is obtained, pre-polymerization multiple is 100 grams of polymer/gram catalyst.
Prepolymerization product and unreacted propylene liguid are discharged by pre-polymerization reactor 101, distribute system into pre-polymerization material
System.Fig. 1 is the schematic diagram of this pre-polymerization material distributing system.The distribution system includes multi-path conversion valve set, by one four
Pass ball valve 103 forms.Pre-polymerization material enters four way ball valve 103 from prepolymer feed inlet 1 through pipeline 1012.Propylene liguid is through liquid
Propylene feed-line 1022 enters four way ball valve 103 from rinse mouth 2.Discharge port 3 is through pipeline 1032 and the second polymer reactor 202
Connection, discharge port 4 are connected to through pipeline 1031 with the first polymer reactor 201.Multi-path is remotely controlled by DCS control system to turn
Valve group is changed, so that pre-polymerization material enters four way ball valve 103 through prepolymer feed inlet 1, enters the second polymerization reaction by discharge port 3
Device 202 (shown in such as Fig. 2 (a)), propylene liguid enter four way ball valve 103 through rinse mouth 2 and enter the first polymerization reaction to discharge port 4
The pipeline 1031 of device 201 rinses；Or pre-polymerization material is made to enter four way ball valve 103 through prepolymer feed inlet 1, by discharge port 4
Into the first polymer reactor 201 (shown in such as Fig. 2 (b)), propylene liguid enters four way ball valve 103 to discharge port 3 through rinse mouth 2
Pipeline 1032 into the second polymer reactor 202 rinses.The four way ball valve is remotely controlled by DCS control system.Pass through journey
The switching cycle time T for setting four way ball valve of sequence software is 6 minute, the wherein time T of A conditionABe 2 minutes, B state when
Between TBIt is 4 minutes.
By pre-polymerization material distributing system, pre-polymerization material is divided into two streams according to 2:1 ratio, respectively enters downstream string
The first polymer reactor 201 and the second polymer reactor 202 of connection.
The production of the PP production line progress homopolymer trade mark.Main polymerized unit technological parameter are as follows: the first polymer reactor
The homopolymerization of 201 progress liquid phases, 70 DEG C of polymerization temperature, polymerization pressure 3.0MPa, polymerization reaction time 40 minutes, produce load 4
Ton/hour.First polymer reactor 201 is connected by connecting pipeline 2011 with the second polymer reactor 202.Second polymerization reaction
Device 202 equally carries out the homopolymerization of liquid phase, and 67 DEG C of polymerization temperature, polymerization pressure 2.7MPa, polymerization reaction time 40 minutes, production is negative
Lotus is 4 ton/hours.Obtained solid polymer and a large amount of unreacted propylene monomer mixture material, into powder scrubbing tower 203
After the catalyst and fine powder that remove short circuit, the evaporation cooling of homopolymerization and propylene liguid is carried out into the first gas-phase reactor 204, is gathered
80 DEG C of temperature, polymerization pressure 1.7MPa, polymerization reaction time 70 minutes are closed, produce load is 6 ton/hours；Solid polymer powder
Material go successively to the second gas-phase reactor 205 carry out homopolymerization, 70 DEG C of polymerization temperature, polymerization pressure 1.5MPa, polymerization reaction time
60 minutes, produce load was 3 ton/hours.Obtained polymer powders carry out gas solid separation through circulation gas separating device, unreacted
Propylene monomer recycling, and solid polymer is washed, carries out granulation packaging after drying, finally obtains homopolypropylene product.It is poly-
The produce load of propylene producing line is 17 ton/hours, and the produce load than the existing method in comparative example 2 improves 42%.
Embodiment 4
80000 tons/year of Hypol technique PP production line, using Two Liquid Phases reaction kettle list gas-phase reactor, process exists
Liquid-phase bulk prepolymerization device and pre-polymerization material distributing system are increased on the basis of existing PP Production Technology process.This
Outside, necessary transformation is carried out to the recirculated water of the propylene feed of second liquid phase kettle, cooling as needed, as needed to the first gas
The propylene feed of phase reaction device, the recirculated water of cooling are transformed.Its flow chart is as shown in Figure 8.
The prepolymerization mode of propylene is continuous liquid-phase bulk prepolymerization.Pre-polymerization reactor 101 is that vertical stirred tank is anti-
Device is answered, so that material in kettle is uniformly mixed simultaneously augmentation of heat transfer using the oblique paddle stirrer of multilayer.By low temperature liquid propylene feed and
Chilled water in 101 collet of pre-polymerization reactor withdraws from polymerization reaction heat.Wherein, low temperature liquid propylene is raw material propylene through being subcooled
But device 102 is cooled to 5 DEG C of propylene, is then divided into two strands, and the propylene through pipeline 1021 goes to pre-polymerization reactor 101, through liquid
The propylene of state propylene feed-line 1022 goes to pre-polymerization material distributing system.Polypropylene catalyst series are by pipeline 1011 and pipe
After the cold propylene of line 1021 converges, into pre-polymerization reactor 101.Recirculated water in 101 collet of pre-polymerization reactor be from
The mixed solution of sub- water and ethylene glycol, temperature is -5 DEG C after ice maker is cooling.10 DEG C of prepolymerization temperature, polymerization pressure 3.4MPa,
The prepolymerization time 10 minutes, propylene pre-polymer is obtained, pre-polymerization multiple is 100 grams of polymer/gram catalyst.
Prepolymerization product and unreacted propylene liguid are discharged by pre-polymerization reactor 101, distribute system into pre-polymerization material
System.Fig. 1 is the schematic diagram of this pre-polymerization material distributing system.The distribution system includes multi-path conversion valve set, by one four
Pass ball valve 103 forms.Pre-polymerization material enters four way ball valve 103 from prepolymer feed inlet 1 through pipeline 1012.Propylene liguid is through liquid
Propylene feed-line 1022 enters four way ball valve 103 from rinse mouth 2.Discharge port 3 is through pipeline 1032 and the second polymer reactor 202
Connection, discharge port 4 are connected to through pipeline 1031 with the first polymer reactor 201.Multi-path is remotely controlled by DCS control system to turn
Valve group is changed, so that pre-polymerization material enters four way ball valve 103 through prepolymer feed inlet 1, enters the second polymerization reaction by discharge port 3
Device 202 (shown in such as Fig. 2 (a)), propylene liguid enter four way ball valve 103 through rinse mouth 2 and enter the first polymerization reaction to discharge port 4
The pipeline 1031 of device 201 rinses；Or pre-polymerization material is made to enter four way ball valve 103 through prepolymer feed inlet 1, by discharge port 4
Into the first polymer reactor 201 (shown in such as Fig. 2 (b)), propylene liguid enters four way ball valve 103 to discharge port 3 through rinse mouth 2
Pipeline 1032 into the second polymer reactor 202 rinses.The four way ball valve is remotely controlled by DCS control system.Pass through journey
The switching cycle time T for setting four way ball valve of sequence software is 6 minute, the wherein time T of A conditionABe 2 minutes, B state when
Between TBIt is 4 minutes.
By pre-polymerization material distributing system, pre-polymerization material is divided into two streams according to 2:1 ratio, respectively enters downstream
First polymer reactor 201 and the second polymer reactor 202.
The production of the PP production line progress homopolymer trade mark.Main polymerized unit technological parameter are as follows: the first polymer reactor
The homopolymerization of 201 progress liquid phases, 70 DEG C of polymerization temperature, polymerization pressure 3.0MPa, polymerization reaction time 40 minutes, produce load 4
Ton/hour.First polymer reactor 201 is connected by connecting pipeline 2011 with the second polymer reactor 202.Second polymerization reaction
Device 202 equally carries out the homopolymerization of liquid phase, and 67 DEG C of polymerization temperature, polymerization pressure 2.7MPa, polymerization reaction time 40 minutes, production is negative
Lotus is 4 ton/hours.Obtained solid polymer and a large amount of unreacted propylene monomer mixture material, into powder scrubbing tower 203
After the catalyst and fine powder that remove short circuit, the evaporation cooling of homopolymerization and propylene liguid is carried out into the first gas-phase reactor 204, is gathered
80 DEG C of temperature, polymerization pressure 1.7MPa, polymerization reaction time 70 minutes are closed, produce load is 6 ton/hours.Obtained polymer
Powder carries out gas solid separation, unreacted propylene monomer recycling through circulation gas separating device, and solid polymer is washed, after drying
Granulation packaging is carried out, homopolypropylene product is finally obtained.14 ton/hours of the production of PP production line, than existing Two Liquid Phases
The operation produce load of the production line of reaction kettle list gas-phase reactor improves 40%.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (11)
1. a kind of liquid phase method polypropylene manufacturing process comprising:
Step A, by polypropylene catalyst and liquid propylene, the raw reaction of hybrid concurrency in pre-polymerization reactor, obtains propylene pre-polymerization
Object；
Pre-polymerization material is divided into multiply logistics according to predetermined ratio in pre-polymerization material distributing system, respectively enters downstream by step B
Multiple series polymerizations reactors；The pre-polymerization material include obtained in step A with propylene pre-polymer active catalyst and
Liquid propene；
Step C, in the multiple series polymerizations reactors in downstream, in liquid propylene medium, homopolymerization or the copolymerization for carrying out propylene are anti-
It answers, obtains polypropylene product；And optionally
The polypropylene product is continued the homopolymerization or copolyreaction of propylene by step D in the gas phase；
Wherein, the pre-polymerization material distributing system includes being equipped with feed inlet, at least one rinse mouth and at least two discharge ports
Multi-path conversion valve set, the pre-polymerization material distributing system are electrically connected with the controller.
2. the method according to claim 1, wherein in step, the temperature of the reaction is -10 to 50 DEG C；
The pressure of the reaction is 1-8MPa.
3. method according to claim 1 or 2, which is characterized in that the polymer reactor be selected from annular-pipe reactor and/or
Tank reactor.
4. method described in any one of -3 according to claim 1, which is characterized in that the upstream of the rinse mouth is equipped with liquid
Propylene feed-line, and the pipeline is connected to rinse mouth.
5. method described in any one of -4 according to claim 1, which is characterized in that in the multi-path conversion valve set,
The feed inlet is connected with pre-polymerization reactor, the discharge port different from downstream polymer reactor connections respectively, it is described go out
It is not connected between material mouth, is not connected between the feed inlet and rinse mouth.
6. method described in any one of -5 according to claim 1, which is characterized in that in the multi-path conversion valve set into
Periodically switching is connected under the control of the controller from different discharge ports respectively for material mouth and rinse mouth, is divided between the period
0.01-60 minutes.
7. method described in any one of -6 according to claim 1, which is characterized in that the multi-path conversion valve set includes extremely
A few four-way valve.
8. method described in -7 according to claim 1, which is characterized in that when the multi-path conversion valve set includes two or two
When the above four-way valve, any discharge port of upstream four-way valve is connected to the feed inlet of downstream four-way valve.
9. method described in any one of -8 according to claim 1, which is characterized in that carry out the copolymerization of copolyreaction with propylene
Monomer is selected from ethylene and C4-C10One of alpha-olefin or a variety of.
10. method described in any one of -9 according to claim 1, which is characterized in that in step C, the temperature of the reaction
Degree is 50-100 DEG C；The pressure of the reaction is 1-8MPa.
11. method described in any one of -10 according to claim 1, which is characterized in that in step D, carry out in the gas phase
Reaction temperature be 50-150 DEG C；The pressure of the reaction carried out in the gas phase is 1-4MPa.
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