CN207685180U - The preparation system of polypropylene or propylene ethylene copolymers - Google Patents
The preparation system of polypropylene or propylene ethylene copolymers Download PDFInfo
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- CN207685180U CN207685180U CN201721493341.2U CN201721493341U CN207685180U CN 207685180 U CN207685180 U CN 207685180U CN 201721493341 U CN201721493341 U CN 201721493341U CN 207685180 U CN207685180 U CN 207685180U
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 59
- 229920005653 propylene-ethylene copolymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 443
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 431
- 239000007791 liquid phase Substances 0.000 claims abstract description 167
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 110
- 238000012685 gas phase polymerization Methods 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 239000002002 slurry Substances 0.000 claims abstract description 72
- -1 polypropylene Polymers 0.000 claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 claims abstract description 46
- 230000006835 compression Effects 0.000 claims abstract description 25
- 238000007906 compression Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000012805 post-processing Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 141
- 239000012071 phase Substances 0.000 claims description 65
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 53
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 53
- 239000004571 lime Substances 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 150000001336 alkenes Chemical class 0.000 claims description 31
- 238000007334 copolymerization reaction Methods 0.000 claims description 27
- 238000004064 recycling Methods 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 238000009834 vaporization Methods 0.000 claims description 15
- 230000008016 vaporization Effects 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000012808 vapor phase Substances 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000001351 cycling effect Effects 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004581 coalescence Methods 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 21
- 229920005604 random copolymer Polymers 0.000 abstract description 14
- 239000002685 polymerization catalyst Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 55
- 238000000034 method Methods 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000011084 recovery Methods 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 27
- 239000000843 powder Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 23
- 238000012662 bulk polymerization Methods 0.000 description 22
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000007872 degassing Methods 0.000 description 12
- 238000006356 dehydrogenation reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
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- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
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- 206010024769 Local reaction Diseases 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
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- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The utility model is related to propylene polymerization fields, disclose polypropylene or the preparation system of propylene ethylene copolymers, including：Prepolymerization unit (A), liquid phase polymerization unit (B), gas-phase polymerization unit (C) and the post-processing unit (D) being sequentially connected to；Prepolymerization unit (A) includes the propylene surge tank (1), propylene compression pump (2) and prepolymerization kettle (3) being sequentially connected to, the propylene of propylene surge tank (1) will be come from, through propylene compression pump (2) boil down to liquid propylene, polymerization catalyst is carried again without condensing unit and is all passed through prepolymerization kettle (3) and carries out Propylene Pre-polymerization, obtains raw slurry；Raw slurry is carried out liquid phase polymerization, gas-phase polymerization and product gas solid separation by liquid phase polymerization unit (B), gas-phase polymerization unit (C) and post-processing unit (D) successively, obtains Noblen or random copolymer.The system reduces propylene polymerization energy consumption of unit product and propylene loss.
Description
Technical field
The utility model is related to propylene polymerizations to industrialize field, and in particular, to one kind carrying out poly- third with three-stage technique
The preparation system of alkene or propylene ethylene copolymers.
Background technology
Polypropylene is using propylene as polymer made of monomer polymerization, is a very important kind in general-purpose plastics,
Its with abundant raw material, it is cheap, be easily worked the characteristics such as molding, nontoxic, can also pass through the measures such as copolymerization, blending, enhancing
It is modified, it is to be only second to the second largest plastics of polyethylene in vistanex to have very wide application field.And
Propylene can also be copolymerized with ethylene, prepare Propylene-ethylene random copolymer.
Producing polyacrylic technology both at home and abroad at present mainly has：Liquid phase noumenal method, gas phase substance law and liquid-phase bulk
The polymerization being in series with gas phase ontology.According to the difference of reactor types, and endless tube method (Spheripol), gas can be divided into
Phase fluidized bed process (Unipol), vertical stirred tank method (Novolen, Hypol), horizontal agitated vessel method (Inoes, JPP) and difference
The combined method of reaction kettle.In the technique for having liquid phase polymerization, polymerisation occurs in the liquid phase, in order to control reaction
Temperature and the degree of polymerization are designed with pre-polymerization, and in the technique of gas-phase polymerization, catalyst and raw material propylene are added directly into reaction
In, do not set pre-polymerization.
In polypropylene production process, propylene monomer is anti-in polymerization under the action of catalyst, activator, electron donor
Progress polymerisation in device is answered to obtain polypropylene slurry or solid material, the polypropylene of generation loses using flash liberation, catalyst
Living, dry and nitrogen displacement, obtains polypropylene powder product, in the propylene gas that reactor discharging is carried secretly in the process, through too low
It compresses and washes and washs, returns to reaction system recycling after the separation of gas compression, light gas, to reduce disappearing for raw material propylene and hydrogen
Consumption.
Current domestic and international polymarization method for prodcing polyacrylates, each own different advantage and disadvantage：
Batch process bulk technique：By the propylene polymerization process of domestic independent development, advantage have flow it is short, investment
Low, quick, disadvantage is that technique is backward, the degree of automation is low, unstable product quality, operating cost are high, poor product quality.
The Spheripol techniques of Lyondell Basell：Ring canal reaction kettle, using axial-flow pump forced circulation, liquid-phase bulk
Polymerization, the chuck outside endless tube remove heat.Its advantage is that reaction condition is relatively easy to control, reactor heat transfer coefficient is big, unit volume production
Rate is high, properties of product are stablized, and the covering of trade mark range is wide；The investment of its disadvantage is big, reaction conversion per pass is low, has large-scale rotation to set
Standby, high energy consumption, the construction period is long, after-treatment system is complicated.
The Unipol techniques of Grace：Gas-phase fluidized-bed reactor, heat of polymerization are taken away by the sensible heat of gas, gas circulation amount
Greatly, need powerful booster fan that could realize, it is less uniform for mixed type, product quality entirely in reaction kettle.Its advantage has suitable
It closes ethylene and propylene is copolymerized, flow is simple, the covering of product good physical performance, the trade mark is wide；Its disadvantage has high energy consumption, equipment size
Greatly, difficulty of processing is high, investment is high, device efficiency is low.
The Innovene techniques of INEOS companies：Using Horizontal stirring reactor and high performance INcat CDi catalyst,
The reactor removes heat close to plug flow reactor, using liquid propylene vaporization.Its advantage has reactor to remove, and the thermal efficiency is high, produces
Smooth operation, residence time of material is uniform in the reaction phase, and the product melting means range of production is wide, energy consumption is relatively low；Its disadvantage has reaction
Hot spot is easy tod produce in kettle and plasticizing block, reactor difficulty of processing height, key equipment need import, investment high.
The Hypol techniques of Mitsui：Liquid-phase bulk and gas phase ontology group technology produce polypropylene, the first two reaction kettle
For vertical stirred tank, latter two is vertical gas fluidised bed polymerisation kettle；Its advantage can produce random copolymerization and block copolymerization product；
Its disadvantage long flow path, device efficiency are low, gas phase reaction is complete mixed type, product quality is uneven, catalyst adaptability is poor, device
Small scale；The Hypol process units without on newly domestic in recent years.
But during above-mentioned polytechnic industrializing implementation, there is acrylic polymers production unit high energy consumption
Defect, and quality and the safety of stability and device operation of polymeric articles are influenced in turn, it is industrialized to increase project
Investment, influences the economic benefit of project.
Utility model content
Purpose of the utility model is to solve the specific energy consumptions for how reducing polypropylene production, improve the quality of product
With the safety of stability and system operation, the problem of reducing the loss of propylene, proposes polypropylene or propylene ethylene copolymers
Preparation system, the equipment that the system coupled propylene prepolymerization, liquid phase bulk propylene polymerization and propylene gas phase bulk polymerization are completed,
The mitigation prepolymerization of propylene may be implemented, reduce catalyst amount, meet the requirement of acrylic polymers product, reduce entire technique
Specific energy consumption in industrializing implementation and propylene loss, improve the economy of propylene industrialized production.
To achieve the goals above, the utility model provides a kind of polypropylene or the preparation system of propylene ethylene copolymers,
The system includes：
Prepolymerization unit A, liquid phase polymerization unit B, gas-phase polymerization unit C and the post-processing unit D being sequentially connected to；
Prepolymerization unit A includes the propylene surge tank 1, propylene compression pump 2 and prepolymerization kettle 3 being sequentially connected to, and will come from propylene
The propylene of surge tank 1 through 2 boil down to liquid propylene of propylene compression pump, then carries olefin polymerization catalysis, activator and electron
Body is all passed through prepolymerization kettle 3 without condensing unit and carries out Propylene Pre-polymerization, obtains the raw material slurry containing propylene pre-polymer
Liquid；
Liquid phase polymerization unit B carries out liquid propylene homopolymerization or the raw slurry and ethylene for the raw slurry
Liquid phase random copolymerization is carried out, liquid phase polymerization product is obtained；
Gas-phase polymerization unit C is used to the liquid phase polymerization product carrying out gas-phase polymerization, obtains Noblen or random
Copolymer；
The product that post-processing unit D is used to obtain gas-phase polymerization carries out gas solid separation, obtains Noblen or random
Copolymer, while isolating propylene gas and returning to liquid phase polymerization unit B.
Preferably, propylene surge tank 1 is arranged the propylene that one is connected to propylene compression pump 2 and exports, and third in propylene surge tank 1
Alkene is passed through prepolymerization kettle 3 merely through propylene compression pump 2.
Preferably, the propylene compression pump 2 in prepolymerization unit A and it is not provided with propylene condensing unit between prepolymerization kettle 3.
Preferably, propylene compression pump 2 is directly connected to prepolymerization kettle 3 by pipeline 100, and alkene is respectively set on pipeline 100
The addition mouth of polymerization catalyst, activator and electron donor.
Preferably, liquid phase polymerization unit B includes slurry line 101, liquid phase polymerizer 4 and propylene vaporization-reuse unit；Slurry
Liquid pipe line 101 is connected to prepolymerization kettle 3 and liquid phase polymerizer 4, and reclaim liquid phase propylene entrance and recycling are provided in slurry line 101
Circulating hydrogen entrance；Propylene vaporization-reuse unit is connected to liquid phase polymerizer 4, is used for liquid propylene vapour in liquid phase polymerizer 4
Change the propylene gas changed into be condensed and be recycled back to liquid phase polymerizer 4.
Preferably, the propylene vaporization-reuse unit includes propylene condenser 6, lime set knockout drum 5, circulating fan 7, with
And the pipeloop 102 of connection lime set knockout drum 5 and circulating fan 7；Propylene condenser 6 is connected to liquid phase polymerizer 4 and lime set point
From tank 5, the part propylene air cooling coalescence for releasing liquid phase polymerizer 4 is sent into lime set knockout drum 5 and carries out gas-liquid separation, point
The liquid propylene separated out returns to liquid phase polymerizer 4；Circulating fan 7 is connected to lime set knockout drum 5 and liquid phase polymerizer 4, for that will coagulate
The propylene gas that liquid knockout drum 5 is isolated returns to liquid phase polymerizer 4.
Preferably, optional ethylene inlet is set on pipeloop 102, is used for propylene-ethylene random copolymerization.
Preferably, gas-phase polymerization unit C includes polypropylene slurry line 103, gas-phase polymerization reactor 8, propylene cycle list
Member and vapor phase polymerizer discharge nozzle 14；
Polypropylene slurry line 103 is connected to liquid phase polymerizer 4 and gas-phase polymerization reactor 8, in polypropylene slurry line 103
Upper setting control valve；
Propylene cycling element is connected to gas-phase polymerization reactor 8, and the propylene for releasing gas-phase polymerization reactor 8 returns
Return propylene gas-phase polymerization.
Preferably, the propylene cycling element includes gas phase kettle propylene condenser 10, propylene lime set tank 11, propylene lime set pump
12 and propylene circulating fan 13；Gas phase kettle propylene condenser 10 is connected to gas-phase polymerization reactor 8 and propylene lime set tank 11, and being used for will
The propylene gas that gas-phase polymerization reactor 8 releases, which condenses and is sent into propylene lime set tank 11, carries out gas-liquid separation, the part isolated
Propylene condensate liquid returns to gas-phase polymerization reactor 8 from the top of gas-phase polymerization reactor 8 and participates in propylene gas-phase polymerization, isolates
Propylene gas is passed through gas-phase polymerization reactor 8 from the lower part of gas-phase polymerization reactor 8 by propylene circulating fan 13 and helps blender gas
Polymer material in phase polymerization reaction device 8.
Preferably, post-processing unit D is connected to by vapor phase polymerizer discharge nozzle 14 with gas-phase polymerization unit C, for that will gather
It closes product and carries out gas solid separation, obtain Noblen or random copolymer；The propylene gas isolated passes through in slurry line 101
Reclaim liquid phase propylene entrance be passed through liquid phase polymerizer 4, the upper fresh hydrogen of the recycling hydrogen isolated mixing passes through slurry line
Recycling circulating hydrogen entrance on 101 is passed through liquid phase polymerizer 4.
Through the above technical solutions, the utility model, which provides one kind, being used for propylene homo or the industrialized liquid of random copolymerization
Phase prepolymerization, liquid-phase bulk polymerization and the combined three stage polymerization system of gas phase bulk polymerization.It is combined by three stage polymerization so that
This system can integrally improve Propylene Pre-polymerization, not need condensing propylene specifically, in system to the condensing unit of sub-zero temperature,
Propylene Pre-polymerization can be carried out at 40~45 DEG C, 3.2~3.9MPaG, and 5~10 DEG C of condition compared with the prior art is more
Mildly.Polymerization catalyst can be taken primary all from prepolymerization addition, catalyst be filled in batches without the prior art, in system
Reduce the addition mouth of setting polymerization catalyst.
Further more, liquid propylene, which may be implemented, in system provided by the utility model once feeds all participation Propylene Pre-polymerizations,
The raw slurry containing the polypropylene prepolymer more preferably disperseed is obtained, only pipeline 100 is connected to 2 He of propylene compression pump in system
Prepolymerization kettle 3, liquid phase, the homogeneous reaction of gas-phase polymerization of subsequent coupling can also be conducive to by simplifying system setting, improve polymer
The quality of product.
Unreacted propylene gas recycling is no longer needed to setting fresh propylene by entire technical process in technical process
Supplement entrance.
Whole system provided by the utility model can reduce units of product energy consumption and propylene loss.After measured, this is used
The system that utility model provides, unit of the product energy consumption can be less than 50kg and mark oil/ton PP powders, and minimum reachable 40kg marks oil/ton
PP powders, unit product processing cost is about the same as the 1/2 of scale same type imported technology product.
In addition the system is avoided that in force the case where hot spot and implode occurs in reaction part, is reduced product and is moulded
Change the probability of block, product particle is non-breakable.The liquid phase polymerization unit of the system removes heat by the way of liquid propylene vaporization, and third
Alkene circulation and stress amount is small, and system is not necessarily to large-scale recycle unit, can effectively reduce system investments, the construction period is short, and economy is more preferable.
Description of the drawings
Fig. 1 is the process flow diagram of the polyacrylic preparation method of the present invention；
Fig. 2 is the process flow diagram of the preparation method of the propylene ethylene copolymers of the present invention.
Reference sign
1- propylene surge tank 2- propylene compression pump 3- prepolymerization kettles
4- liquid phase polymerizer 5- lime set knockout drum 6- propylene condensers
7- circulating fan 8- gas-phase polymerization reactor 9- blenders
10- gas phase kettle propylene condenser 11- propylene lime set tank 12- propylene lime sets pump
13- propylene circulating fan 14- vapor phase polymerizer discharge nozzle 100- pipelines
101- stock line 102- pipeloop 103- polypropylene slurry lines
15- degassing cabin 16- drier 17- deactivators
18- drier filters 19- replaces kettle 20- nitrogen heaters
21- water sealed tank 22- water scrubber 23- propylene recovery compressors
24- washing pump 25- oil scrubber 26- oil washes pumps
27- propylene gas surge tank 28- propylene air compressor 29- high pressure propylene washing towers
30- dehydrogenation tower 31- propylene lime set tank 32- Propylene recovery lime sets pump
33- Propylene recovery condenser 34- circulating hydrogen surge tank 35- circulating hydrogen compressors
36- hydrogen gas buffer 37- reboiler 38- oil scrubber condensers
39- water scrubber condenser 40- cyclone separators
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The utility model provides a kind of polypropylene or the preparation system of propylene ethylene copolymers, and as shown in Figure 1 and Figure 2, this is
System includes：
Prepolymerization unit A includes the propylene surge tank 1, propylene compression pump 2 and prepolymerization kettle 3 being sequentially connected to, and will come from propylene
The propylene of surge tank 1 through 2 boil down to liquid propylene of propylene compression pump, then carries olefin polymerization catalysis, activator and electron
Body is all passed through prepolymerization kettle 3 without condensing unit and carries out Propylene Pre-polymerization, obtains the raw material slurry containing propylene pre-polymer
Liquid；
Liquid phase polymerization unit B carries out liquid propylene homopolymerization or the raw slurry and ethylene for the raw slurry
Liquid phase random copolymerization is carried out, liquid phase polymerization product is obtained；
Gas-phase polymerization unit C is used to the liquid phase polymerization product carrying out gas-phase polymerization, obtains Noblen or random
Copolymer.
In the utility model, liquid phase prepolymerization, liquid-phase bulk polymerization and the combined three stage polymerization of gas phase bulk polymerization are taken
System can allow the propylene feed in prepolymerization unit A before prepolymerization reactor 3 to be improved.Preferably, propylene surge tank 1
The propylene outlet of one connection propylene compression pump 2 is set, and the propylene in propylene surge tank 1 is passed through pre- merely through propylene compression pump 2
Poly- kettle 3.Prepolymerization is carried out with the prior art only part propylene raw material, another part is fed directly to downstream without prepolymerization
Liquid phase or gas-phase polymerization are different, and propylene feedstocks may be implemented all by prepolymerization in system provided by the utility model, reduce control
System operation, and catalytic systems for polymerization of olefins is made preferably to disperse in propylene feedstocks.
In the utility model, further, take three stage polymerization system that can reduce the requirement of prepolymerization condition.It is preferred that
Ground is not provided with propylene condensing unit between the propylene compression pump 2 and prepolymerization kettle 3 in prepolymerization unit A.Preferably, liquid propylene
Pressure is 4~4.5MPaG, and liquid propylene temperature is 40~45 DEG C.System provided by the utility model can allow propylene liquid phase
Prepolymerization carries out at 40~45 DEG C, the low temperature prepolymerization generally carried out at 5~10 DEG C or so higher than the prior art.It can reduce
Condensing steps simultaneously reduce corresponding energy consumption and operation needs.
It in the utility model, can simply be connected between propylene compression pump 2 and prepolymerization kettle 3, reduce industrial construction expense.It is excellent
Selection of land, propylene compression pump 2 and prepolymerization kettle 3 are directly connected to by pipeline 100, be respectively set on pipeline 100 olefin polymerization catalysis,
The addition mouth of activator and electron donor.
In the utility model, it can be gone successively to through the raw slurry containing propylene pre-polymer that prepolymerization unit A is obtained
Further polymerization reaches the industrial polymeric articles needed to improve for liquid phase polymerization and the concatenated polymerization process of gas-phase polymerization.It is preferred that
Ground, liquid phase polymerization unit B include slurry line 101, liquid phase polymerizer 4 and propylene vaporization-reuse unit；Slurry line 101 connects
Logical prepolymerization kettle 3 and liquid phase polymerizer 4, are provided with reclaim liquid phase propylene entrance in slurry line 101 and recycling circulating hydrogen enters
Mouthful；Propylene vaporization-reuse unit is connected to liquid phase polymerizer 4, for liquid propylene in liquid phase polymerizer 4 to be vaporized change into third
Alkene gas is condensed and is recycled back to liquid phase polymerizer 4.
In the utility model, liquid phase polymerizer 4 can select vertical stirred autoclave, with cycle water leg.Blade
Stirring make reaction evenly, while the heat transfer between strength imparting material prevents local reaction from overheating and luming.It is gas in polymeric kettle
Liquid two-phase coexistent is not necessarily to powerful hybrid control device, and equipment production intensity is big, and reaction operating mode is easy to control.According to production
Product or scale are different, and polymeric kettle can also be arranged more parallel connections, system production capacity can be adjusted flexibly, can also be wanted according to owner
The polypropylene product for production multimodal of seeking survival.
In the utility model, liquid phase polymerization unit B can take the side using the liquid propylene vaporization in liquid phase polymerizer 4
The heat that propylene polymerization releases is removed in formula help, while the propylene vaporized can pass through the propylene vaporization-reuse list
Member recycling, and yield can be reduced compared with prior art, to reduce the industrialization investment of recycle unit.Preferably, described
Propylene vaporization-reuse unit includes propylene condenser 6, lime set knockout drum 5, circulating fan 7, and 5 He of connection lime set knockout drum
The pipeloop 102 of circulating fan 7；Propylene condenser 6 is connected to liquid phase polymerizer 4 and lime set knockout drum 5, is used for liquid phase polymerization
The part propylene air cooling coalescence that kettle 4 releases is sent into lime set knockout drum 5 and carries out gas-liquid separation, the liquid propylene rework solution isolated
Phase-polymerization kettle 4；Circulating fan 7 is connected to lime set knockout drum 5 and liquid phase polymerizer 4, the propylene for isolating lime set knockout drum 5
Gas returns to liquid phase polymerizer 4.In the propylene vaporization-reuse unit, the liquid phase that can will be directly condensed out with propylene condenser 6
Propylene returns to liquid phase polymerizer 4.The part propylene gas that liquid phase polymerizer 4 releases can be sent directly into the participation of lime set knockout drum 5
Gas-liquid separation.
In the utility model, it is preferable that optional ethylene inlet is set on pipeloop 102, it is random for propylene-ethylene
Copolymerization.
In the utility model, can propylene homo or nothing further be continued by the gas-phase polymerization unit C of the system
Rule copolymerization.Preferably, gas-phase polymerization unit C includes polypropylene slurry line 103, gas-phase polymerization reactor 8, propylene cycling element
With vapor phase polymerizer discharge nozzle 14；Polypropylene slurry line 103 is connected to liquid phase polymerizer 4 and gas-phase polymerization reactor 8, poly- third
Control valve is set in alkene slurry line 103；Propylene cycling element is connected to gas-phase polymerization reactor 8, is used for gas-phase polymerization
The propylene that reactor 8 releases returns to propylene gas-phase polymerization.
In the utility model, gas-phase polymerization reactor 8 can be selected the horizontal reactor of belt stirrer 9, material in reactor
It is big, adaptable to the slightly tacky material such as high melting means and copolymer that residence time is uniformly, equipment produces intensity；Blender 9 can
To use "ON" type structure, powder is made to be uniformly mixed.Gas-phase polymerization reactor 8 has chuck recirculated water to realize that reaction heat is removed.Gas
Radioactivity level-sensing device is also set up in phase polymerization reaction device 8 or by electric current come the material position of control material.Gas-phase polymerization reactor 8 can
Wise temperature automatic control system is arranged, 6~8 temperature control areas can be divided into according to reactor scale.Blender 9 has simultaneously to be stirred
The function of mixing and push powder product to move forward, specific paddle angle according to reaction kettle scale and residence time not
Together.
In the utility model, the propylene cycling element can recycle gas-phase polymerization reactor 8 release it is unreacted
Propylene, and partially recycled propylene can be returned to the stirring being used to help in gas-phase polymerization reactor 8 with gas phase.It is preferred that
Ground, the propylene cycling element include gas phase kettle propylene condenser 10, propylene lime set tank 11, propylene lime set pump 12 and propylene cycle
Wind turbine 13；Gas phase kettle propylene condenser 10 is connected to gas-phase polymerization reactor 8 and propylene lime set tank 11, is used for gas phase polymerization
The propylene gas that device 8 releases condense and be sent into propylene lime set tank 11 carry out gas-liquid separation, the part propylene condensate liquid isolated from
The top of gas-phase polymerization reactor 8 returns to gas-phase polymerization reactor 8 and participates in propylene gas-phase polymerization, and the propylene gas isolated is by third
Alkene circulating fan 13 is passed through gas-phase polymerization reactor 8 from the lower part of gas-phase polymerization reactor 8 and helps stirred gas-phase polymerization reactor 8
In polymer material.
In the utility model, it is preferable that post-processing unit D passes through vapor phase polymerizer discharge nozzle 14 and gas-phase polymerization unit C
Connection, for polymerizate to be carried out gas solid separation, obtains Noblen or random copolymer；The propylene gas isolated passes through
Reclaim liquid phase propylene entrance in slurry line 101 is passed through liquid phase polymerizer 4, the upper fresh hydrogen of recycling hydrogen mixing isolated
Gas is passed through liquid phase polymerizer 4 by the recycling circulating hydrogen entrance in slurry line 101.
Specifically, post-processing unit D includes drying device and gas separating and reclaiming device.
The drying device includes：Inside carries the degassing cabin 15 of cyclone separator 40 and bag filter, setting is lost
The drier 16 of device 17 and filter 18 living, carries water scrubber at the displacement kettle 19 for being connected with nitrogen heater 20 and water sealed tank 21
The water scrubber 22 and propylene recovery compressor 23 of condenser 39 and washing pump 24.
Wherein, degassing cabin 15 by from vapor phase polymerizer discharge nozzle 14 containing Noblen product or contain propylene and ethylene
The product of random copolymer carries out gas solid separation, and the propylene gas isolated is passed through the gas separating and reclaiming device, isolates
Polymer powders are passed through deactivator 17；
Degassing is dried in deactivated polymer powder from deactivator 17 by drier 16, and the gas of abjection is through filter
18 are passed through gas through water scrubber 22, and dry polymer powders are passed through displacement kettle 19；
The polymer powders of the drying are subjected to the hot nitrogen that nitrogen heater 20 provides, abjection micro third by displacement kettle 19
Final polypropylene or propylene-ethylene copolymers are obtained after alkene gas；The propylene gas of abjection high idle discharge after water sealed tank 21, spark arrester
It puts；
Gas is passed through propylene recovery compressor 23 after the washing of the gas of water scrubber inherent filtration in 22 future device 18, then can be with
Direct Propylene recovery is used for other processes.
The gas separating and reclaiming device includes：With oil scrubber condenser 38 and oil wash pump 26 oil scrubber 25, carry
High pressure propylene washing tower 29, dehydrogenation tower 30 and the propylene condensate pipe 31 of reboiler 37.
Wherein, the alkyl aluminum and oligomer of the propylene gas washing removing entrainment that oil scrubber 25 isolates degassing cabin 15 etc. are miscellaneous
The white oil containing antistatic agent may be used as cleaning solvent in matter.
In the utility model, oil scrubber 25 is connected to by propylene gas surge tank 27, the propylene air compressor 28 being sequentially communicated
High pressure propylene washing tower 29 will be sent into high pressure propylene washing tower 29 by the gas of white oil washing.In high pressure propylene washing tower 29
The unreacted propylene gas of the discharge of partial gas phase polymer reactor 8 can also be added.29 bottom of tower of high pressure propylene washing tower can arrange
Go out the Propylene recovery that part is used for other processes.
In the utility model, dehydrogenation tower 30 is connected to the tower top of high pressure propylene washing tower 29, and tower top fixed gas is isolated richness
Hydrogen and propylene lime set.Dehydrogenation tower 30 passes through the Propylene recovery condenser 33, circulating hydrogen surge tank 34, recycle hydrogen that are sequentially communicated
Air compressor 35 and hydrogen gas buffer 36 are connected with the recycling circulating hydrogen entrance in slurry line 101, by the hydrogen rich gas
Fresh hydrogen is passed through liquid phase polymerizer 4 as circulating hydrogen in mixing.The setting connection of propylene lime set tank 31 is under dehydrogenation tower 30
Face, for containing the propylene lime set.Propylene lime set tank 31 passes through returning in 32 connection slurry line 101 of Propylene recovery lime set pump
Cycle propylene entrance is received, for returning to liquid phase polymerizer 4 using the propylene lime set as recycling cycle propylene.
The course of work combination Fig. 1, Fig. 2 of polypropylene provided by the utility model or the preparation system of propylene ethylene copolymers
It is described in further detail.
(I) it stocks up：
It is up to the fresh propylene that polymerization requires and enters propylene surge tank 1, then go out from unique propylene of propylene surge tank 1
Mouth, which conveys propylene, to be forced into 4~4.5MPaG into propylene compression pump 2 and obtains the liquid propylene that temperature is 40~45 DEG C.Liquid phase
Propylene is conveyed by pipeline 100 into prepolymerization kettle 3, meanwhile, olefin polymerization catalysis, activator and electron donor pass through pipeline 100
On respective addition mouth be mixed into liquid propylene, under the carrying of liquid propylene enter prepolymerization kettle 3.
Because the utility model is by Propylene Pre-polymerization unit A, liquid phase polymerization unit B and gas-phase polymerization unit C during this
It is combined, propylene feedstocks can be made to be not necessarily to frozen cooling equipment, and can all feed into Propylene Pre-polymerization excessively, final propylene
The whole preparation process of homopolymerization or random copolymerization reduces energy consumption and propylene loss.
(II) paradigmatic system：
(1) Propylene Pre-polymerization：In prepolymerization kettle 3, liquid propylene is in olefin polymerization catalysis, activator and electron donor
Effect is lower to carry out Propylene Pre-polymerization reaction.Prepolymerization kettle 3 carries blender, and prepolymerization temperature is 40~45 DEG C, and pre-polymerization resultant pressure is
3.2~3.9MPaG, prepolymerization residence time are about 4~5min, and the polymerization multiple for obtaining propylene pre-polymer is about 50~100 times.
Prepolymerization kettle is fed：Olefin polymerization catalysis (Ti catalyst) is about 0.04~0.06 weight % of liquid propylene, work
Agent (triethyl aluminum) be about 0.2~0.4 weight % of liquid propylene, electron donor (Cyclohexyl Methyl Dimethoxysilane) about
For 0.04~0.06 weight % of liquid propylene.
(2) liquid phase bulk propylene polymerization：
(a) liquid phase homopolymerization：Raw slurry containing propylene pre-polymer is obtained by prepolymerization kettle 3, is mixed into back through slurry line 101
Receive liquid propylene, hydrogen becomes liquid phase polymerization raw material, polyacrylic a concentration of 150~300g/L in liquid phase polymerization raw material；Recycling
The addition of liquid propylene is 25~30 weight % of liquid propylene；Relative to the 1000kg polypropylene in liquid phase polymerization raw material,
The addition of hydrogen is 0.04~0.3kg.Liquid phase polymerizer 4 is the vertical reactor with stirring.
Liquid phase polymerization raw material enters liquid phase polymerizer 4 and carries out propylene liquid phase homopolymerization.Propylene liquid phase homopolymerization temperature is 65~70
DEG C, propylene liquid phase homopolymerization pressure is 3~3.8MPaG, residence time about 40min.The material of liquid phase polymerization raw material in liquid phase polymerizer 4
45~57 volume %s of the position control in liquid phase polymerizer 4.The reaction heat of liquid phase homopolymerization can be by liquid propylene vaporization and folder
Set recirculated water is taken away, wherein the part propylene gas after vaporization, after the cooling of propylene condenser 6, part directly rework solution is met
Kettle 4 is closed, enters lime set knockout drum after partly being mixed (from liquid phase polymerizer 4 and propylene condenser 6) with uncooled propylene gas
5, the liquid propylene through isolating returns in liquid phase polymerizer 4, and the gas phase isolated is passed through is communicated to cycle through pipeloop 102
Wind turbine 7 returns after supercharging and is bubbled in the liquid phase of liquid phase polymerizer 4, gas and reaction solution can on the one hand mixed uniformly, a side
Face makes gas reduce the liquidus temperature among polymeric kettle, and the pressure of liquid phase polymerizer 4 is come also by the amount of external circulation cooling system
Control；
(b) random copolymerization：Be passed through ethylene on pipeloop 102, ethylene feed amount be 5 weight % of liquid propylene with
Under, preferably 1~3 weight % may be implemented propylene and carry out liquid phase random copolymerization in liquid phase polymerizer 4 with ethylene, with production
Random copolymerization product.
(3) propylene gas phase bulk polymerization：
(i) gas-phase homopolymerization：The polypropylene slurries (containing propylene and polypropylene) being discharged from liquid phase polymerizer 4 are logical by pressure difference
It crosses and enters gas-phase polymerization reactor 8 with valvular polypropylene slurry line 103, wherein the unreacted propylene carried secretly continues
Polymerisation is polypropylene；Gas-phase polymerization temperature is 80~95 DEG C, and reaction pressure is 2.5~2.8MPaG, and polypropylene slurries are in gas
Residence time in phase polymerization reaction device 8 is about 45~60min, obtains the product containing Noblen.Alternatively,
(ii) gas phase random copolymerization：Be discharged from liquid phase polymerizer 4 copolymer slurries (containing propylene and propylene-ethylene without
Advise copolymer) rely on pressure difference by entering gas-phase polymerization reactor 8 with valvular polypropylene slurry line 103, wherein pressing from both sides
The unreacted propylene of band carries out gas phase random copolymerization with ethylene；Gas phase random copolymerization temperature is 80~95 DEG C, and gas phase is randomly total
Poly- pressure is 2.5~2.8MPaG；The residence time of gas phase random copolymerization is about 45~60min；It obtains randomly total containing propylene and ethylene
The product of polymers.
The material position of material can be controlled by radioactivity level-sensing device or electric current in gas-phase polymerization reactor 8, and material position is general
Control is in 35~60 volume %.Gas-phase polymerization reactor 8 can be selected the horizontal reactor of belt stirrer 9, material in reactor
It is big, adaptable to the slightly tacky material such as high melting means and copolymer that residence time is uniformly, equipment produces intensity；Blender 9 can
To use "ON" type structure, powder is made to be uniformly mixed.Polymerization reaction heat in gas-phase polymerization reactor 8 can pass through propylene Quench
The vaporization of liquid and chuck recirculated water are taken away；Unreacted gas (mainly propylene gas, ethylene tolerance is few to participate in copolymerization completely) is logical
After crossing the settling section settlement section powder on 8 top of gas-phase polymerization reactor, a part of gas is returned by adjusting to be distributed to propylene
Receipts system, another part gas enter propylene lime set tank 11 after the cooling of gas phase kettle propylene condenser 10, isolate propylene and swash
Cold liquid is returned by propylene lime set pump 12 to gas-phase polymerization reactor 8, is reabsorbed polymerisation thermal evaporation and is withdrawn reaction heat.Propylene
The gas that lime set tank 11 is isolated is sent after the supercharging of propylene circulating fan 13 to the bottom of gas-phase polymerization reactor 8, i.e. reuse
Propylene again fluidizes the polypropylene powder inside gas-phase polymerization reactor 8, removes heat to help system and reduces reaction kettle
Power of agitator.Whether this wind circulating system is arranged, and can be determined according to the scale of gas-phase polymerization reactor 8.Gas-phase polymerization reactor 8
Wise temperature automatic control system may be used, 6~8 temperature control areas can be divided into according to reactor scale.Blender 9 has simultaneously
Stirring and the function of pushing powder product to move forward, specific paddle angle according to reaction kettle scale and residence time
It is different.
(III) post-processing of the product containing Noblen or the product containing propylene-ethylene random copolymer：
(first) gas solid separation：By from vapor phase polymerizer discharge nozzle 14 containing Noblen product (containing propylene gas,
Hydrogen, polypropylene) or product (containing propylene gas, hydrogen, propylene-ethylene copolymers) containing propylene-ethylene random copolymer, according to
Depended on pressure enters degassing cabin 15 through exporting powder control valve, and the product goes out in vapor phase polymerizer discharge nozzle 14 for pulse mode
Material.
15 inside of degassing cabin is arranged to separate and recover the cyclone separator 40 and bag filter of the dust in propylene gas；
The polymer powders that degassing cabin 15 separates, to deactivator 17, are passed through suitable steam by gravity fall in deactivator 17
The catalyst carried secretly in the product is inactivated, the powder inactivated enters drier 16 and degassing is dried, further
Propylene recovery.
Drier 16 is a horizontal indirectly heat blade stirring drier, and hollow hot axis and external jacket are passed through low pressure
Steam is thermally dried wet mash by wall, while wet stock can also be moved to material outlet, drier 16 by agitating shaft
Operation temperature is 100~105 DEG C, and pressure is micro-positive pressure.
(second) harvests polymeric articles：Powder after inactivation, drying falls on displacement kettle 19 by gravity under drier 16,
The hot nitrogen provided with nitrogen heater 20 in displacement kettle 19 is further backing out the denier propylene gas carried secretly in powder；It excludes
Gas after water sealed tank 21, spark arrester high-altitude qualified discharge；Powder after degassing is sent by nitrogen supply air system after
Continuous workshop section, obtains final polypropylene or propylene-ethylene copolymers product.
(the third) gas recovery：Wet mash heats the propylene gas released in drier 16, enters through filter 18 and washes
Tower 22 washs, and water scrubber 22 is used as washing medium using desalted water, the denier hydrogen chloride of entrained catalyst decomposition in gas, because
The hydrochloric acid in appropriate alkaline liquor and in water is added in desalted water in this, propylene gas after washing after the cooling of water scrubber cooler 39, then
It is recycled after the pressurization of propylene recovery compressor 23, can be used for sending outside.
The Propylene recovery gas for leaving degassing cabin 15 enters the washing of oil scrubber 25, then through propylene gas surge tank 27, propylene gas
Compressor 28 enters high pressure propylene washing tower 29 after compressing；The tower top fixed gas that 29 tower top of high pressure propylene washing tower is isolated enters
Dehydrogenation tower 30 removes hydrogen rich gas, and the recovered propylene condenser 33 of hydrogen rich gas returns to dehydrogenation tower condensation and separation of liquid propylene
30；The hydrogen rich gas is mixed with the fresh hydrogen after metering, then successively through circulating hydrogen surge tank 34, circulating hydrogen compressor 35
It is sent after pressurization and hydrogen gas buffer 36 to liquid phase polymerizer 4 and is utilized；30 bottom of tower lime set of dehydrogenation tower is buffered into propylene lime set tank 31, so
It uses 32 pressurization rear portion of Propylene recovery lime set pump to return to liquid phase polymerizer 4 afterwards to utilize, a part is used as high pressure propylene washing tower
29 overhead reflux liquid；Leave the propylene (about 19 weight % of propane content) for containing a large amount of propane in 29 bottom of tower of high pressure propylene washing tower
Battery limit (BL) processing is sent out after being mixed after filtering with the aqueous propylene that propylene recovery compressor 23 pressurizes.
Wherein, oil scrubber 25 is the plate column of a top tape washing oil tower condenser 38, inside it with containing antistatic agent
White oil propylene gas is washed, to deviate from the impurity such as the alkyl aluminum carried secretly in propylene gas and oligomer.High pressure third
Alkene scrubbing tower 29 is the sieve plate distillation column that a bottom carries reboiler 37, is flowed back with the propylene lime set of propylene lime set tank 31
Liquid, to detach the propane in propylene, propane is accumulated in anti-locking system；Dehydrogenation tower 30 is connected after high pressure propylene washing tower 29
Sieve-plate tower, using the lime set body of Propylene recovery condenser 33 as the propylene in the phegma of dehydrogenation tower 30 cooling dehydrogenation tower 30,
To detach the hydrogen rich gas contained in propylene gas, 30 bottom of dehydrogenation tower is direct-connected logical with propylene lime set tank 31, straight after the liquid condensing that flows back
It connects and enters propylene lime set tank 31.
The utility model will be described in detail by embodiment below.
Embodiment 1
(1) prepolymerization
By propylene pressurize pressure about 4.2MPaG, temperature be about 42 DEG C liquid propylene；Using liquid propylene as carrier,
Be separately added into content in liquid propylene be the Ti catalyst (CS-1) of 0.04 weight %, 0.3 weight % triethyl aluminum and
The Cyclohexyl Methyl Dimethoxysilane of 0.05 weight %；So all it is directly inputted in prepolymerization kettle and forms polymeric size, then
Propylene Pre-polymerization is carried out under the conditions of 42 DEG C, 3.2MPaG, residence time 4min, polyacrylic polymerization in obtained raw slurry
Multiple is 75 times；
(2) liquid-phase bulk polymerization
Reclaim liquid phase propylene is added in the raw slurry that (1) obtains and hydrogen blendes together liquid phase polymerization raw material (wherein polypropylene
A concentration of 200g/L, reclaim liquid phase propylene addition is about 25 weight % of liquid propylene, added hydrogen 0.08kg/
1000kg polypropylene), propylene liquid phase homopolymerization is carried out at 68 DEG C, 3MPaG, material position is 45 volume % in reaction kettle, is stopped
40min；
In propylene liquid phase homopolymerization process, partially polymerized reaction heat is taken away in the vaporization of Partial Liquid Phase propylene.The propylene gas of vaporization passes through
Recycling returns to propylene liquid phase homopolymerization with gas phase or liquid phase.
(3) gas phase bulk polymerization
The polypropylene slurries that (2) are obtained are added in gas phase bulk polymerization device, and third is carried out at 90 DEG C, 2.6MPaG
Alkene gas-phase homopolymerization, residence time 45min, material position is 55 volume % in reactor.
In propylene gas phase homopolymerization process, the unreacted propylene gas in part of discharge is recovered, and third is returned with gas phase or liquid phase
Alkene gas-phase homopolymerization.
Complete propylene gas-phase homopolymerization after, the obtained product containing Noblen after subsequent drying and propylene recovery,
Polypropylene product and propylene are isolated, propylene recovery continues on for the propylene liquid phase homopolymerization of step (2).
It calculates in above-mentioned entire technical process, the specific energy consumption for producing Noblen is that 42kg marks oil/ton PP powders.It is raw
1000kg polypropylene is produced, propylene loss is 4kg.
Embodiment 2
(1) prepolymerization
By propylene pressurize pressure about 4MPaG, temperature be about 45 DEG C liquid propylene；Using liquid propylene as carrier, point
Be not added content in liquid propylene be the Ti catalyst (CS-1) of 0.06 weight %, 0.2 weight % triethyl aluminum and
The Cyclohexyl Methyl Dimethoxysilane of 0.06 weight %；Then all it is directly inputted in prepolymerization kettle and forms polymeric size, connects
It and carries out Propylene Pre-polymerization under the conditions of 45 DEG C, 3.6MPaG, residence time 4min, it is polyacrylic poly- in obtained raw slurry
It is 50 times to close multiple；
(2) liquid-phase bulk polymerization
It is (wherein polyacrylic dense that raw slurry addition Propylene recovery and hydrogen that (1) obtains are blended together into liquid phase polymerization raw material
Degree is 150g/L, and Propylene recovery addition is about 27 weight % of liquid propylene, and added hydrogen is 0.12kg/1000kg poly- third
Alkene), propylene liquid phase homopolymerization is carried out at 70 DEG C, 3.5MPaG, material position is 60 volume % in reaction kettle, stops 35min；
In propylene liquid phase homopolymerization process, partially polymerized reaction heat is taken away in the vaporization of Partial Liquid Phase propylene.The propylene gas of vaporization passes through
Recycling returns to propylene liquid phase homopolymerization with gas phase or liquid phase.
(3) gas phase bulk polymerization
The polypropylene slurries that (2) are obtained are added in gas phase bulk polymerization device, and third is carried out at 80 DEG C, 2.7MPaG
Alkene gas-phase homopolymerization, residence time 60min, material position is 45 volume % in reactor.
In propylene gas phase homopolymerization process, the unreacted propylene gas in part of discharge is recovered, and third is returned with gas phase or liquid phase
Alkene gas-phase homopolymerization.
Complete propylene gas-phase homopolymerization after, the obtained product containing Noblen after subsequent drying and propylene recovery,
Polypropylene product and propylene are isolated, propylene recovery continues on for the propylene liquid phase homopolymerization of step (2).
It calculates in above-mentioned entire technical process, the specific energy consumption for producing Noblen is that 45kg marks oil/ton PP powders.It is raw
1000kg polypropylene is produced, propylene loss is 5kg.
Embodiment 3
(1) prepolymerization
By propylene pressurize pressure about 4.5MPaG, temperature be about 40 DEG C liquid propylene；Using liquid propylene as carrier,
Be separately added into content in liquid propylene be the Ti catalyst (CS-1) of 0.05 weight %, 0.4 weight % triethyl aluminum and
The Cyclohexyl Methyl Dimethoxysilane of 0.04 weight %；Then all it is directly inputted in prepolymerization kettle and forms polymeric size, connects
It and carries out Propylene Pre-polymerization under the conditions of 40 DEG C, 3.8MPaG, residence time 5min, it is polyacrylic poly- in obtained raw slurry
It is 100 times to close multiple；
(2) liquid-phase bulk polymerization
It is (wherein polyacrylic dense that raw slurry addition Propylene recovery and hydrogen that (1) obtains are blended together into liquid phase polymerization raw material
Degree is 300g/L, and Propylene recovery addition is about 30 weight % of liquid propylene, and added hydrogen is 0.2kg/1000kg poly- third
Alkene), propylene liquid phase homopolymerization is carried out at 69 DEG C, 3.7MPaG, material position is 40 volume % in reaction kettle, stops 45min；
In propylene liquid phase homopolymerization process, partially polymerized reaction heat is taken away in the vaporization of Partial Liquid Phase propylene.The propylene gas of vaporization passes through
Recycling returns to propylene liquid phase homopolymerization with gas phase or liquid phase.
(3) gas phase bulk polymerization
The polypropylene slurries that (2) are obtained are added in gas phase bulk polymerization device, and third is carried out at 95 DEG C, 2.8MPaG
Alkene gas-phase homopolymerization, residence time 48min, material position is 50 volume % in reactor.
In propylene gas phase homopolymerization process, the unreacted propylene gas in part of discharge is recovered, and third is returned with gas phase or liquid phase
Alkene gas-phase homopolymerization.
Complete propylene gas-phase homopolymerization after, the obtained product containing Noblen after subsequent drying and propylene recovery,
Polypropylene product and propylene are isolated, propylene recovery continues on for the propylene liquid phase homopolymerization of step (2).
It calculates in above-mentioned entire technical process, the specific energy consumption for producing Noblen is that 50kg marks oil/ton PP powders.It is raw
1000kg polypropylene is produced, propylene loss is 5kg.
Embodiment 4
(1) prepolymerization
By propylene pressurize pressure about 4.2MPaG, temperature be about 42 DEG C liquid propylene；Using liquid propylene as carrier,
Be separately added into content in liquid propylene be the Ti catalyst (CS-1) of 0.04 weight %, 0.3 weight % triethyl aluminum and
The Cyclohexyl Methyl Dimethoxysilane of 0.05 weight %；Then all it is directly inputted in prepolymerization kettle and forms polymeric size, connects
It and carries out Propylene Pre-polymerization under the conditions of 42 DEG C, 3.2MPaG, residence time 4min, it is polyacrylic poly- in obtained raw slurry
It is 75 times to close multiple；
(2) liquid-phase bulk polymerization
It is (wherein polyacrylic dense that raw slurry addition Propylene recovery and hydrogen that (1) obtains are blended together into liquid phase polymerization raw material
Degree is 200g/L, and Propylene recovery addition is about 25 weight % of liquid propylene, and added hydrogen is 0.08kg/1000kg poly- third
Alkene).The ethylene of 3 weight % of liquid propylene is added on the pipeloop 102 of Propylene recovery gas, is carried out at 68 DEG C, 3MPaG
Propylene, ethylene liquid phase random copolymerization, material position is 45 volume % in reaction kettle, stops 40min；
During liquid phase random copolymerization, partially polymerized reaction heat is taken away in the vaporization of Partial Liquid Phase propylene.The propylene gas of vaporization passes through
Recycling returns to liquid phase random copolymerization with gas phase or liquid phase.
(3) gas phase bulk polymerization
The copolymer slurries that (2) are obtained are added in gas phase bulk polymerization device, and third is carried out at 90 DEG C, 2.6MPaG
Alkene, ethylene gas phase random copolymerization, residence time 45min, material position is 55 volume % in reactor；
During propylene, ethylene gas phase random copolymerization, the unreacted propylene gas in part of discharge is recovered, with gas phase or liquid
Mutually return to gas phase random copolymerization.
The obtained product containing propylene-ethylene random copolymer isolates propylene second after subsequent drying and propylene recovery
Olefinic random copolymer product and propylene, propylene recovery continue on for the liquid phase random copolymerization of step (2).
It calculates in above-mentioned entire technical process, the specific energy consumption for producing propylene-ethylene random copolymer is that 42kg marks oil/ton
PP-PE powders, produce 1000kg Propylene-ethylene random copolymers, and propylene loss is 4kg.
Comparative example 1
(1) prepolymerization
Take -5 DEG C, 50 weight % of the liquid propylene of 3.81MPaG mixed with polymerization catalyst, contain in polymerization catalyst
The Ti catalyst (CS-1) of the 0.08 weight % on the basis of whole liquid propylenes, the triethyl aluminum and 0.08 weight of 0.5 weight %
The Cyclohexyl Methyl Dimethoxysilane of % to be measured, is added in pre-polymerization endless tube and carries out low temperature prepolymerization, prepolymerization temperature is about 10 DEG C,
Pre-polymerization resultant pressure is about 3.8MPaG, residence time 12min, and polyacrylic polymerization multiple is about 60 in obtained raw slurry
Times；
(2) liquid-phase bulk polymerization
By raw material slurry and remaining 50 weight % liquid propylenes, (0.08kg/ is added in polyacrylic a concentration of 50 weight %
The polyacrylic hydrogen of 1000kg) it is mixed into liquid phase polymerization raw material, subsequently into the first annular-pipe reactor, in liquid phase polymerization raw material
A part of propylene polymerize, and remaining liquid makes the material in reactor be in paste-like as the diluent of polymer, passes through
Axial-flow pump beats cycle, keeps slurry flow at high speed in the reactor and is uniformly mixed；
The slurry in the first annular-pipe reactor is continuously sent into the second annular-pipe reactor by the industrial siding that discharges again and is continued
It carries out liquid phase polymerization and supplements fresh propylene (addition is 25 weight % of liquid propylene).First and second annular-pipe reactor reacts
Temperature is about 70~73 DEG C, and reaction pressure is about 3.8MPaG, residence time about 1h.
The polymerisation slurry being discharged from the second annular-pipe reactor obtains polypropylene powder after flash distillation, degassing, drying, inactivation
Material.The obtained gas that deaerates send reaction system reuse after propylene recovery.
By calculating above-mentioned endless tube propylene polymerization processes, the specific energy consumption for producing Noblen is about 70kg mark oil/tons
PP powders, produce 1000kg polypropylene, and propylene loss is 5kg.
Above-mentioned annular-pipe reactor and technique are to use more propene polymerization reactor and technique both at home and abroad at present, due to ring
Pipe reactor removes heat and all realizes that slurry in ring Bottomhole pressure is realized by axial-flow pump promotion by chuck recirculated water, and poly- third
Alkene slurry is liquid phase flash distillation discharging, must increase steam-heating system, further increase the energy consumption of the technological reaction process.
Comparative example 2
Propylene pressurization is reached 3.5MPa and condensed to liquid phase after -5 DEG C and is entered in the poly- kettle of prepolymerization, with polymerization catalyst
(including Ti catalyst (CS-1), triethyl aluminum, Cyclohexyl Methyl Dimethoxysilane) is contacted at 0 DEG C, and catalyst components exist
Content in liquid propylene is the triethyl aluminum and 0.08 weight % of the Ti catalyst (CS-1) of 0.08 weight %, 0.5 weight %
Cyclohexyl Methyl Dimethoxysilane, be used in combination blender to pinch material mixing, herein generate catalyst activated centre, then open
The pre-polymerization of beginning propylene, prepolymerized residence time are 5min, and polyacrylic polymerization multiple is 75 times in obtained raw slurry.
What prepolymerization obtained enters containing active catalyst and propylene mixtures slurry in liquid phase polymerizer, 69 DEG C,
1~1.6h is stopped under 3.4MPa, and the reaction was continued.A concentration of 130g/L of polypropylene, propylene total amount are 10t/h in slurry, hydrogen is added
Amount is 150L/min.Material position is 45 volume % in liquid phase reactor kettle.
Polymerization catalyst is also added in liquid phase polymerization：Ti catalyst (CS-1) 0.4g/h, triethyl aluminum 3L/h, cyclohexyl first
Base dimethoxysilane 0.4L/h.
The slurry of liquid phase polymerizer discharge enters gas phase reaction kettle, and gas phase bulk polymerization is carried out at 90 DEG C, 2.8MPa, is stopped
Stay the time for 1.5h, material position is 40 volume % in gas phase reaction kettle.
The product containing Noblen for completing to obtain after gas-phase polymerization is isolated after subsequent drying and propylene recovery
Polypropylene product and propylene, propylene recovery continue on for the liquid phase bulk propylene polymerization of step (2).
It calculates in above-mentioned entire technical process, the specific energy consumption for producing Noblen is that 60kg marks oil/ton PP powders.It is raw
1000kg polypropylene is produced, propylene loss is 6kg.
System provided by the utility model is can be seen that by the result of above-described embodiment and comparative example, and propylene may be implemented
Prepolymerization, the combination of liquid phase bulk propylene polymerization and propylene gas phase bulk polymerization, Propylene Pre-polymerization process simplification is without propylene
Condensation, can once whole liquid propylenes and polymerization catalyst charging, and olefin polymerization catalysis can reduce addition, can be with
Whole propylene are involved in pre-polymerization merging and carry out Propylene Pre-polymerization under 40~45 DEG C of mild temperature, obtain propylene pre-polymer dispersion
Better raw slurry improves product quality, can reduce energy consumption of unit product and the propylene loss of propylene polymerization.
Need propylene to condense to subzero in comparative example 1, and can only Partial Liquid Phase propylene carry out low temperature prepolymerization；Polymerization process
In need to add fresh propylene and polymerization catalyst, product needs flash distillation process, the propylene polymerization unit product of entire technical process
Energy consumption and propylene loss are high.
In comparative example 2, the prior art needs propylene to condense to subzero, and prepolymerization temperature is low, and catalyst charge is high,
Also polymerization catalyst is added, propylene polymerization energy consumption of unit product and the propylene loss for completing entire technical process are high.
Preferred embodiments of the present invention, still, the utility model and unlimited are described in detail above in association with attached drawing
In this.In the range of the technology design of the utility model, a variety of simple variants can be carried out to the technical solution of the utility model,
It is combined with any other suitable method including each technical characteristic, these simple variants and combination equally should be considered as this
Utility model disclosure of that, belongs to the scope of protection of the utility model.
Claims (10)
1. the preparation system of a kind of polypropylene or propylene ethylene copolymers, which is characterized in that the system includes：
Prepolymerization unit (A), liquid phase polymerization unit (B), gas-phase polymerization unit (C) and the post-processing unit (D) being sequentially connected to；
Prepolymerization unit (A) includes the propylene surge tank (1), propylene compression pump (2) and prepolymerization kettle (3) being sequentially connected to, and will be come from
The propylene of propylene surge tank (1) through propylene compression pump (2) boil down to liquid propylene, then carries olefin polymerization catalysis, activator
And electron donor, it is all passed through prepolymerization kettle (3) without condensing unit and carries out Propylene Pre-polymerization, obtains containing propylene pre-polymer
Raw slurry；
Liquid phase polymerization unit (B) for the raw slurry carry out liquid propylene homopolymerization or the raw slurry and ethylene into
Row liquid phase random copolymerization, obtains liquid phase polymerization product；
Gas-phase polymerization unit (C) is used to the liquid phase polymerization product carrying out gas-phase polymerization；
The product that post-processing unit (D) is used to obtain gas-phase polymerization carries out gas solid separation, obtains Noblen or random total
Polymers, while isolating propylene gas and returning to liquid phase polymerization unit (B).
2. system according to claim 1, which is characterized in that a connection propylene compression pump is arranged in propylene surge tank (1)
(2) propylene exports, and the propylene in propylene surge tank (1) is passed through prepolymerization kettle (3) merely through propylene compression pump (2).
3. system according to claim 1 or 2, which is characterized in that propylene compression pump (2) in prepolymerization unit (A) and
Prepolymerization kettle is not provided with propylene condensing unit between (3).
4. system according to claim 3, which is characterized in that propylene compression pump (2) and prepolymerization kettle (3) pass through pipeline
(100) it is directly connected to, the addition mouth of olefin polymerization catalysis, activator and electron donor is respectively set on pipeline (100).
5. system according to claim 1, which is characterized in that liquid phase polymerization unit (B) includes slurry line (101), liquid
Phase-polymerization kettle (4) and propylene vaporization-reuse unit；
Slurry line (101) is connected to prepolymerization kettle (3) and liquid phase polymerizer (4), and reclaim liquid phase is provided in slurry line (101)
Propylene entrance and recycling circulating hydrogen entrance；
Propylene vaporization-reuse unit is connected to liquid phase polymerizer (4), for turning liquid propylene vaporization in liquid phase polymerizer (4)
At propylene gas condensed and be recycled back to liquid phase polymerizer (4).
6. system according to claim 5, which is characterized in that the propylene vaporization-reuse unit includes propylene condenser
(6), lime set knockout drum (5), circulating fan (7), and it is connected to the pipeloop of lime set knockout drum (5) and circulating fan (7)
(102)；
Propylene condenser (6) is connected to liquid phase polymerizer (4) and lime set knockout drum (5), for release liquid phase polymerizer (4)
Part propylene air cooling coalescence is sent into lime set knockout drum (5) and carries out gas-liquid separation, and the liquid propylene isolated returns to liquid phase polymerizer
(4)；
Circulating fan (7) is connected to lime set knockout drum (5) and liquid phase polymerizer (4), and third for isolating lime set knockout drum (5)
Alkene gas returns to liquid phase polymerizer (4).
7. system according to claim 5, which is characterized in that optional ethylene inlet is arranged on pipeloop (102), uses
In propylene-ethylene random copolymerization.
8. system according to claim 1, which is characterized in that gas-phase polymerization unit (C) includes polypropylene slurry line
(103), gas-phase polymerization reactor (8), propylene cycling element and vapor phase polymerizer discharge nozzle (14)；
Polypropylene slurry line (103) is connected to liquid phase polymerizer (4) and gas-phase polymerization reactor (8), in polypropylene slurry line
(103) control valve is set on；
Propylene cycling element is connected to gas-phase polymerization reactor (8), for returning the propylene that gas-phase polymerization reactor (8) releases
Return propylene gas-phase polymerization.
9. system according to claim 8, which is characterized in that the propylene cycling element includes gas phase kettle propylene condenser
(10), propylene lime set tank (11), propylene lime set pump (12) and propylene circulating fan (13)；
Gas phase kettle propylene condenser (10) is connected to gas-phase polymerization reactor (8) and propylene lime set tank (11), is used for gas-phase polymerization
The propylene gas that reactor (8) releases, which condenses and is sent into propylene lime set tank (11), carries out gas-liquid separation, the part propylene isolated
Condensate liquid returns to gas-phase polymerization reactor (8) from the top of gas-phase polymerization reactor (8) and participates in propylene gas-phase polymerization, isolates
Propylene gas is passed through gas-phase polymerization reactor (8) from the lower part of gas-phase polymerization reactor (8) by propylene circulating fan (13) and helps
Polymer material in stirred gas-phase polymerization reactor (8).
10. system according to claim 8, which is characterized in that post-processing unit (D) passes through vapor phase polymerizer discharge nozzle
(14) it is connected to gas-phase polymerization unit (C), for polymerizate to be carried out gas solid separation, obtains Noblen or random copolymerization
Object；The propylene gas isolated is passed through liquid phase polymerizer (4) by the reclaim liquid phase propylene entrance in slurry line (101), separation
The upper fresh hydrogen of recycling hydrogen mixing gone out, liquid phase polymerization is passed through by the recycling circulating hydrogen entrance in slurry line (101)
Kettle (4).
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| WO2022250822A1 (en) * | 2021-05-24 | 2022-12-01 | Exxonmobil Chemical Patents Inc. | Biphasic polymerization processes |
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