CN115141299A - Process system and method for continuously producing polyolefin elastomer - Google Patents
Process system and method for continuously producing polyolefin elastomer Download PDFInfo
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- CN115141299A CN115141299A CN202210724685.9A CN202210724685A CN115141299A CN 115141299 A CN115141299 A CN 115141299A CN 202210724685 A CN202210724685 A CN 202210724685A CN 115141299 A CN115141299 A CN 115141299A
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- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims description 45
- 230000008569 process Effects 0.000 title claims description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 239000002994 raw material Substances 0.000 claims abstract description 72
- 239000000047 product Substances 0.000 claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000009833 condensation Methods 0.000 claims abstract description 35
- 230000005494 condensation Effects 0.000 claims abstract description 35
- 238000001704 evaporation Methods 0.000 claims abstract description 30
- 230000008020 evaporation Effects 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 239000003054 catalyst Substances 0.000 claims description 53
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 48
- 238000007670 refining Methods 0.000 claims description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 20
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 18
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 10
- -1 3, 5-di-tert-butyl salicylidene Chemical group 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- 239000012968 metallocene catalyst Substances 0.000 claims description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 5
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 5
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 5
- 239000001282 iso-butane Substances 0.000 claims description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 5
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 230000006324 decarbonylation Effects 0.000 claims description 4
- 238000006606 decarbonylation reaction Methods 0.000 claims description 4
- 238000006298 dechlorination reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 230000000415 inactivating effect Effects 0.000 claims description 4
- 230000000937 inactivator Effects 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- IEVJIMWHPIWBIS-UHFFFAOYSA-N n,n-dihexadecylaniline Chemical compound CCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCC)C1=CC=CC=C1 IEVJIMWHPIWBIS-UHFFFAOYSA-N 0.000 claims description 2
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000005498 polishing Methods 0.000 abstract description 8
- 239000013589 supplement Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 238000010924 continuous production Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- LQZDXSATRKTKIF-UHFFFAOYSA-L CCC(C)(C(C)(C)C)N[Ti+2](C1C=CC=C1)[SiH](C)C.[Cl-].[Cl-] Chemical compound CCC(C)(C(C)(C)C)N[Ti+2](C1C=CC=C1)[SiH](C)C.[Cl-].[Cl-] LQZDXSATRKTKIF-UHFFFAOYSA-L 0.000 description 3
- BHTKQUGPJWEUOJ-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 Chemical compound C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 BHTKQUGPJWEUOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- NQYKSVOHDVVDOR-UHFFFAOYSA-N n-hexadecylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCC NQYKSVOHDVVDOR-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/30—Driving arrangements; Transmissions; Couplings; Brakes
- B01F35/32—Driving arrangements
- B01F35/32005—Type of drive
- B01F35/3204—Motor driven, i.e. by means of an electric or IC motor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1856—Stationary reactors having moving elements inside placed in parallel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a production system of a polyolefin elastomer, which comprises a first reaction kettle; the second reaction kettle is connected with the first reaction kettle in series or in parallel; the first reaction kettle and the second reaction kettle are provided with three-blade flat pushing paddles and three-blade inclined blade turbine paddles; the heat exchanger is connected with the second reaction kettle; a flash tank connected to the heat exchanger; a condensation kettle connected with the flash evaporation kettle; a product tank connected to the coagulum kettle. The invention adopts two kettle type reactors in series/parallel connection for use, and improves the problem that the polymer is adhered to the kettle by improving the measures such as stirring paddles, mirror polishing of the kettle wall and the like; more importantly, the invention adopts a jacket type special structure at the connection part of the product and hot water, and the product which is blown out from the inner pipe wall is washed by the hot water and enters a condensation kettle to be stirred, granulated and devolatilized. In addition, the refined raw material tank provided by the invention is provided with a differential pressure liquid level meter, and the liquid level meter is interlocked with the pump, so that automatic liquid supplement can be realized.
Description
Technical Field
The invention belongs to the technical field of preparation of ethylene/alpha-olefin elastomers, relates to a production system and a production process of a polyolefin elastomer, and particularly relates to a process system and a method for continuously producing the polyolefin elastomer.
Background
Polyolefin elastomer (POE) refers to a random copolymer elastomer of ethylene and long-chain alpha-olefin (1-butene, 1-hexene, 1-octene, etc.), and POE also has excellent performances of aging resistance, ozone resistance, chemical medium resistance, etc., and the heat-resistant temperature of the material is improved by crosslinking POE, so that the main mechanical properties of tensile strength, tear strength, etc. are improved to a great extent. At present, polyolefin elastomers are mainly used widely as adhesives, hot melt adhesives, ink additives, waterproof coiled materials, toughening materials and the like, wherein the polyolefin elastomers are used as the toughening materials in a main use mode of modified polypropylene or polyethylene. Polyolefin elastomers are generally copolymers of two or more olefins with low or no melting point and low glass transition temperatures. Typical polyolefin plastics, such as high density polyethylene, linear low density polyethylene, isotactic polypropylene, and the like, can be produced by liquid phase bulk polymerization, gas phase polymerization, slurry polymerization, and other processes, such as Unipol process, spheripol process, novolene process, and the like, wherein a gas olefin raw material is converted into polymer particles under the action of a supported catalyst, the polymer particles keep shapes in a reactor, and do not stick to the reactor, and the polymer is discharged from the reactor in the form of particles. However, for ethylene/α -olefin elastomers, when the polymerization temperature is between 60 ℃ and 190 ℃, the resulting polymer has viscosity, morphology cannot be maintained, and the reactor can be seriously blocked, especially, at present, POE is mainly produced by a high-temperature solution polymerization process, and due to the presence of long-chain branches, products are easy to swell in a solvent and agglomerate, and the high viscosity causes the phenomenon of reactor sticking or rod climbing in the reactor, thereby affecting continuous production. On the other hand, because POE has the characteristics of high elasticity and good toughness, the devolatilization process is complex and the energy consumption is high.
The prior art also discloses some corresponding improvement modes, for example, patent CN110016092 discloses a method for continuously preparing polyolefin elastomer and a mixture thereof, wherein a kettle-type reactor is adopted for prepolymerization, a static mixer is adopted for static mixing polymerization, and a reaction screw extruder is adopted for extrusion polymerization, so that the problem that the polyolefin elastomer product cannot be continuously polymerized due to overhigh viscosity is solved, but the process has high production difficulty and is difficult to control; the problems of low reaction efficiency, easy crosslinking during copolymerization, easy degradation of polymer chains, coupling change and the like exist in the processing process. And as CN110016090, the continuous production of the polyolefin elastomer is realized by controlling the material viscosity through 3 different reactors and different temperature zones and using the traditional devolatilization and granulation equipment. However, the process has the disadvantages of high investment cost, high energy consumption, complex polymer devolatilization, granulation and molding processing processes, and difficulty in continuous large-scale production.
Therefore, in order to satisfy the characteristics of ethylene/α -olefin elastomers, it is necessary to develop a new process suitable for continuous production, and solving the above problems of the prior art has become one of the problems to be solved by many front-line researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a production system and a production process for polyolefin elastomer, and particularly to a continuous production system for polyolefin elastomer. The device for preparing the thermoplastic elastomer (POE) by copolymerizing the ethylene and the long-chain alpha-olefin is realized by a complete system consisting of a raw material refining unit, a catalyst preparation unit, a reaction unit, a product separation unit and a public unit, and the process is mainly optimized and improved in the reaction unit and the product separation unit, so that continuous production is realized.
The present invention provides a production system for polyolefin elastomer, comprising:
a first reaction kettle;
the second reaction kettle is connected with the first reaction kettle in series or in parallel;
the first reaction kettle and the second reaction kettle are provided with three-blade flat pushing paddles and three-blade inclined blade turbine paddles;
the heat exchanger is connected with the second reaction kettle;
a flash evaporation kettle connected with the heat exchanger;
a condensation kettle connected with the flash evaporation kettle;
a product tank connected to the coagulum kettle.
Preferably, the flash evaporation kettle is connected with the condensation kettle through a jacket type pipeline;
the jacket type pipeline comprises a product inner pipe and a circulating hot water outer pipe;
one end of the product inner tube is communicated with the flash evaporation kettle, and the end close to the condensation kettle is sealed;
the tube wall of the product inner tube is provided with a plurality of holes;
one end of the circulating hot water outer pipe is communicated with the condensation kettle.
Preferably, the product tank has a multi-layer filtration device;
the bottom of the product tank is connected with the circulating hot water outer pipe;
the inner wall of the reaction kettle is a reaction kettle with a mirror polished surface;
one or more of a pressure gauge, a safety valve, a pressure sensor and a temperature probe are arranged on the reaction kettle;
the three-blade inclined blade turbine paddle comprises three-blade 45-degree inclined blade turbine paddles.
Preferably, the production system further comprises a premixing kettle;
the premixing kettle is connected with the first reaction kettle;
the first reaction kettle and the second reaction kettle are used independently or in series/parallel connection;
the production system further comprises a raw material refining unit;
the raw material refining unit comprises one or more of a deoxygenation tower, a dehydration tower, a desulfurization tower, a dechlorination tower and a decarbonylation tower.
Preferably, the production system further comprises a raw material unit;
the raw material unit comprises an ethylene raw material tank, a comonomer raw material tank, a solvent tank and a toluene tank;
the ethylene raw material tank is connected with the premixing kettle through a first raw material refining unit in the raw material refining units;
the comonomer raw material tank is connected with the premixing kettle through a second raw material refining unit in the raw material refining units;
the solvent tank is connected with the premixing kettle through a third raw material refining unit in the raw material refining unit.
Preferably, the production system further comprises a main catalyst tank, a main catalyst configuration tank, a cocatalyst tank and a cocatalyst configuration tank;
the main catalyst tank is respectively connected with the first reaction kettle and the second reaction kettle;
the cocatalyst tank is respectively connected with the first reaction kettle and the second reaction kettle;
the main catalyst configuration tank is connected with the main catalyst tank;
the cocatalyst configuration tank is connected with the cocatalyst tank;
and the toluene tank is respectively connected with the main catalyst configuration tank and the cocatalyst configuration tank through a fourth raw material refining unit in the raw material refining unit.
Preferably, the production system further comprises a deactivator tank and an antioxidant tank;
the inactivator tank is connected to the production system through a connecting pipeline between the second reaction kettle and the heat exchanger;
the antioxidant tank is connected to the production system through a connecting pipeline between the heat exchanger and the flash evaporation kettle;
the condensation kettle comprises a stirring granulation condensation kettle;
the condensate is connected to the product tank by overflow.
The invention provides a production process of a polyolefin elastomer, which comprises the following steps:
1) Premixing ethylene, comonomer and solvent, and then adding a main catalyst and a cocatalyst to carry out polymerization reaction to obtain a reaction product;
2) And (3) carrying out heat exchange on the reaction product obtained in the step and the inactivating agent, adding the antioxidant for flash evaporation, and then granulating to obtain the polyolefin elastomer.
Preferably, the solvent used comprises one or more of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, a mixture of isomeric saturated alkanes, and toluene;
the comonomer comprises one or more of 1-butene, 1-hexene, 1-octene and 1-decene;
the catalyst comprises one or more of a constrained geometry catalyst, a bridged metallocene catalyst, and a non-metallocene catalyst;
the cocatalyst comprises one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dihexadecylphenylammonium tetrakis (pentafluorophenyl) borate;
the production process is a production process for continuously producing the polyolefin elastomer.
Preferably, the pressure of the ethylene is 1.0-15.0 MPa;
the catalyst specifically comprises one or more of dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-titanium dichloride, dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-dimethyl titanium, diphenyl carbon bridging group-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride and [ N- (3, 5-di-tert-butyl salicylidene) -2-diphenyl phosphorus phenyl imine ] titanium trichloride;
the temperature of the polymerization reaction is 60-250 ℃;
the time of the polymerization reaction is 5-30 min;
the polymerization reaction includes a first polymerization reaction and a second polymerization reaction.
The invention provides a production system of a polyolefin elastomer, which comprises a first reaction kettle; the second reaction kettle is connected with the first reaction kettle in series or in parallel; the first reaction kettle and the second reaction kettle are provided with three-blade flat pushing paddles and three-blade inclined blade turbine paddles; the heat exchanger is connected with the second reaction kettle; a flash evaporation kettle connected with the heat exchanger; a condensation kettle connected with the flash evaporation kettle; a product tank connected to the coagulum kettle. Compared with the prior art, the invention aims at the problems that the existing polyolefin elastomer is mainly produced by a high-temperature solution polymerization process, the product is easy to swell in a solvent and agglomerate due to the existence of the long-chain branch, and the continuous production is influenced because the phenomenon of kettle sticking or rod climbing occurs in a reaction kettle due to high viscosity.
The invention especially designs a process system and a method for continuously producing polyolefin elastomer, the invention adopts two kettle type reactors to be used in series/parallel connection, and the problem that polymer is adhered to a kettle is improved by improving the measures of stirring paddles, mirror polishing of the kettle wall and the like; more importantly, the invention adopts a jacket type special structure at the connecting part of the product and hot water, and the hot water flushes the product emerging from the inner pipe wall into a condensation kettle for stirring, granulating and devolatilizing. In addition, the refined raw material tank provided by the invention is provided with a differential pressure liquid level meter, and the liquid level meter is interlocked with the pump, so that automatic liquid supplement can be realized.
The invention firstly greatly improves the problem that the polymer is stuck to the kettle by improving the measures of stirring paddles, mirror polishing of the kettle wall and the like; simultaneously, two kettle type reactors which can be used in series/parallel connection are adopted, so that the reaction operation is simpler and more convenient; on the other hand, because POE has the characteristics of high elasticity and good toughness, the devolatilization process is complex, and the energy consumption of the traditional devolatilization, granulation and molding processing system is high, so that continuous large-scale production is not easy to realize. The invention improves the jacket type special structure, uses hot water to wash the product emerging from the inner pipe wall into the condensation kettle, and greatly reduces the processing cost through stirring, granulating and devolatilizing. In addition, the process is improved, the computer automatic control monitoring operation is adopted, a differential pressure liquid level meter arranged in the refining raw material tank is interlocked with a pump, automatic liquid supplement is realized, and the labor cost is effectively reduced.
The industrial verification result shows that the process system and the method provided by the invention are adopted to continuously produce the polyolefin elastomer, and the polymerization activity is 5 multiplied by 10 7 -10 8 kg/(mol.h), the conversion rate of ethylene per pass is 50-57%, and the conversion rate of 1-octene is 15-25%; the weight average molecular weight of the polyolefin elastomer was 25.3X 10 4 -32×10 4 Molecular weight distribution of 2.7 to 5.6, mol of 1-octeneThe molar insertion rate is 11-15%; the content of VOCs in the POE product is 500ppm.
Drawings
FIG. 1 is a schematic process flow diagram of a process system for continuously producing a polyolefin elastomer according to the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention is preferably carried out in industrial purity or in a purity conventional in the field of production of polyolefin elastomers.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
All the processes and equipment of the present invention, the acronyms of which are common acronyms in the art, each acronym being clearly defined in the field of its associated use, will enable one skilled in the art to understand the common process steps and equipment structure from the acronyms.
The present invention provides a production system of a polyolefin elastomer, comprising:
a first reaction kettle;
the second reaction kettle is connected with the first reaction kettle in series or in parallel;
the first reaction kettle and the second reaction kettle are provided with three-blade flat pushing paddles and three-blade inclined blade turbine paddles;
the heat exchanger is connected with the second reaction kettle;
a flash tank connected to the heat exchanger;
a condensation kettle connected with the flash evaporation kettle;
a product tank connected to the coagulum kettle.
In the present invention, the flash evaporation kettle is preferably connected to the condensation kettle through a jacket type pipeline.
In the present invention, the jacket-type piping preferably includes a product inner pipe and a circulating hot water outer pipe.
In the present invention, one end of the product inner tube is preferably in communication with the flash evaporation kettle, and the end close to the condensation kettle is sealed.
In the present invention, the product inner tube preferably has a plurality of holes on the tube wall.
In the present invention, one end of the outer pipe of the circulating hot water is preferably communicated with the coagulation tank.
In the present invention, the product tank preferably has a multi-layer filtering device.
In the present invention, the bottom of the product tank is preferably connected to the outer pipe of the circulating hot water.
In the invention, the inner wall of the reaction kettle is preferably a reaction kettle after mirror polishing.
In the invention, the reaction kettle is preferably provided with one or more of a pressure gauge, a safety valve, a pressure sensor and a temperature probe, and more preferably provided with the pressure gauge, the safety valve, the pressure sensor or the temperature probe.
In the present invention, the three-bladed inclined blade turbine paddle preferably comprises a three-bladed 45 ° inclined blade turbine paddle.
In the present invention, the production system preferably includes a premix kettle.
In the present invention, the premixing kettle is preferably connected to the first reaction kettle.
In the present invention, the first reaction vessel and the second reaction vessel are preferably used individually or in series/parallel. Specifically, when the reaction kettle is used independently, the feeding of the raw material refining unit and the subsequent heat exchanger of the reaction kettle are connected with a single reaction kettle.
In the present invention, the production system preferably includes a raw material refining unit.
In the present invention, the raw material refining unit includes one or more of a deoxygenation tower, a dehydration tower, a desulfurization tower, a dechlorination tower, and a decarbonylation tower.
In the present invention, the production system preferably includes a raw material unit.
In the present invention, the feed unit preferably includes an ethylene feed tank, a comonomer feed tank, a solvent tank, and a toluene tank.
In the present invention, the ethylene raw material tank is preferably connected to the premix kettle through a first raw material purification unit among the raw material purification units.
In the present invention, the comonomer feed tank is preferably connected to the premix kettle through a second raw material purification unit among the raw material purification units.
In the present invention, the solvent tank is preferably connected to the premix kettle through a third raw material refining unit in the raw material refining unit.
In the present invention, the production system preferably includes a main catalyst tank, a main catalyst arrangement tank, a co-catalyst tank, and a co-catalyst arrangement tank.
In the present invention, the main catalyst tank is preferably connected to the first reaction vessel and the second reaction vessel, respectively.
In the present invention, the cocatalyst tank is preferably connected to the first reaction tank and the second reaction tank, respectively.
In the present invention, the main catalyst configuration tank is preferably connected to the main catalyst tank.
In the present invention, the cocatalyst configuration tank is preferably connected to the cocatalyst tank.
In the present invention, the toluene tank is preferably connected to the main catalyst disposition tank and the co-catalyst disposition tank, respectively, through a fourth raw material purification unit among the raw material purification units.
In the present invention, the production system preferably includes a deactivator tank and an antioxidant tank.
In the invention, the inactivating agent tank is preferably connected to the production system through a connecting pipeline between the second reaction kettle and the heat exchanger.
In the invention, the antioxidant tank is preferably connected to a production system through a connecting pipeline between the heat exchanger and the flash evaporation kettle.
In the present invention, the coagulation vessel preferably includes a stirring granulation coagulation vessel.
In the present invention, the condensate is preferably connected to the product tank by overflow.
In the present invention, the production system is a continuous production system.
The invention is a complete and detailed integral technical scheme, which better improves the continuity and stability of the production of the polyolefin elastomer, and the production system of the polyolefin elastomer can specifically comprise the following components:
the invention provides a device for preparing a thermoplastic elastomer (POE) by copolymerizing ethylene and long-chain alpha-olefin, which is realized by a complete system consisting of a raw material refining unit, a catalyst preparation unit, a reaction unit, a product separation unit and a part of public units, wherein the process is mainly optimized and improved in the reaction unit and the product separation unit, so that the continuous production is realized:
a raw material refining unit: raw materials in the raw material tank are pressurized by a diaphragm pump and then are refined by a deoxygenation tower, a dehydration tower, a desulfurization tower, a dechlorination tower and a decarbonylation tower respectively, the raw materials are refined and then enter a refined raw material storage tank, the refined raw material storage tank is provided with a differential pressure liquid level meter, and the liquid level meter is interlocked with a pump, so that the raw materials can be automatically refined; the refined gas raw material can directly enter a premixing kettle, and the refined liquid raw material needs to be pressurized by a buffer tank through a diaphragm pump again and then enters the premixing kettle or a glove box for catalyst preparation. Meanwhile, an online water and oxygen detection probe is arranged behind the refining tower, and if the water and oxygen in the refined raw material are more than 1ppm, the refined raw material can return to the raw material tank through a return pipeline for refining again. For the raw material with high impurity content, a double-system refining mode combining off-line refining and on-line refining can be adopted, so that the used raw material is ensured to reach the standard.
Catalyst and process for preparing same a preparation unit: the preparation of the main catalyst and the cocatalyst is completed in the glove box, and 2 sets of the main catalyst and cocatalyst preparation tanks in the glove box can realize the quick switching between different main/cocatalyst. Weighing a certain amount of catalyst and solvent, adding into a preparation tank with a stirrer, stirring for 1 hour, and conveying the prepared catalyst solution to a closed buffer tank outside a glove box. Catalyst solution in the buffer tank is pressurized by the diaphragm pump according to experiment requirements and then is conveyed to a corresponding reaction kettle to participate in reaction, a pressure gauge and a transparent window are arranged on the tank, and the catalyst flow is monitored at any time by the electronic scale and the DCS system.
A reaction unit: the materials enter the premixing kettle from the bottom end, are fully mixed and then enter the reaction kettle, and the main catalyst and the cocatalyst solution are also fed from the bottom of the reaction kettle. The effective volumes of the two kettles are both used in series/parallel connection of 1L, the length-diameter ratio of an inner cavity is 1.6, the maximum working pressure of the reaction kettle is 200bar, the maximum working temperature is 300 ℃, each kettle is provided with a three-blade flat push paddle and a 45-degree inclined blade turbine paddle with three blades, and the inner wall of the reaction kettle is subjected to mirror surface polishing. The reaction kettle is provided with a pressure gauge, a safety valve, a pressure sensor and a temperature probe, and is connected with the DCS system to monitor the pressure and temperature changes in the kettle at any time.
In the invention, each kettle is provided with a three-blade flat pushing slurry and a three-blade 45-degree inclined blade turbine blade, and the problem of polymer sticking to the kettle is solved by improving the stirring slurry and the mirror polishing of the kettle wall; and the working pressure and temperature range of the reaction kettle are wider, and the viscosity of a reaction system can be reduced by combining a supercritical polymerization technology.
A product separation unit: the reaction product is heated by a heat exchanger and then enters a flash evaporation kettle for solvent separation, the pressure of the system is reduced, the solvent is rapidly vaporized, the gas-phase material flashed out enters the heat exchanger for condensation and then enters a gas-liquid separation tank for gas-liquid separation, the non-condensable gas is directly discharged after being pressurized by a back pressure valve, and the liquid enters a solvent recovery tank through the interlocking control of a differential pressure liquid level meter and a liquid level regulating valve.
In the invention, the high-viscosity product after flash evaporation and circulating hot water enter from the lower end of the condensation kettle, the connection part of the product and the hot water is of a jacket type special structure, a small pipe in the condensation kettle is used for conveying the product, a pipe head is blocked, a pipe wall is perforated, a large pipe on the outer wall is used as a jacket for conveying the circulating hot water. And products emerging from the inner pipe wall are flushed by hot water, enter the condensation kettle, are stirred and granulated, then overflow into the product tank, are filtered in the product tank, and are conveniently cleaned at regular intervals due to the design of a drawer type product tank. And flushing the product emerging from the inner pipe wall with hot water, feeding the product into a condensation kettle, and stirring and granulating to obtain the polyolefin elastomer.
The invention provides a production process of a polyolefin elastomer, which comprises the following steps:
1) Premixing ethylene, comonomer and solvent, and then adding a main catalyst and a cocatalyst to carry out polymerization reaction to obtain a reaction product;
2) And (3) carrying out heat exchange on the reaction product obtained in the step and the inactivating agent, adding the antioxidant for flash evaporation, and then granulating to obtain the polyolefin elastomer.
The invention firstly mixes ethylene, comonomer and solvent, then adds main catalyst and catalyst promoter to carry out polymerization reaction, and obtains the reaction product.
In the present invention, the solvent used preferably includes one or more of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, a mixture of isomeric saturated alkanes, and toluene, and more preferably isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, a mixture of isomeric saturated alkanes, or toluene.
In the present invention, the comonomer preferably comprises one or more of 1-butene, 1-hexene, 1-octene and 1-decene, more preferably 1-butene, 1-hexene, 1-octene or 1-decene.
In the present invention, the catalyst preferably comprises one or more of a constrained geometry catalyst, a bridged metallocene catalyst and a non-metallocene catalyst, more preferably a constrained geometry catalyst, a bridged metallocene catalyst or a non-metallocene catalyst.
In the present invention, the cocatalyst preferably comprises one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and N, N-dihexadecylammonium tetrakis (pentafluorophenyl) borate, more preferably triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, dichloroethylaluminum, methylaluminoxane, modified methylaluminoxane, perfluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate or N, N-dihexadecylammonium tetrakis (pentafluorophenyl) borate.
In the present invention, the production process is preferably a production process for continuously producing a polyolefin elastomer.
In the present invention, the pressure of ethylene is preferably 1.0 to 15.0MPa, more preferably 4.0 to 12.0MPa, and still more preferably 7.0 to 9.0MPa.
In the present invention, the catalyst specifically preferably includes one or more of dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, diphenylcarbaryl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride and [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphino-phenylimine ] titanium trichloride, and more preferably dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, diphenylcarbaryl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride or [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphino-phenylimine ] titanium trichloride.
In the present invention, the temperature of the polymerization reaction is preferably 60 to 250 ℃, more preferably 100 to 210 ℃, and still more preferably 140 to 170 ℃.
In the present invention, the time for the polymerization reaction is preferably 5 to 30min, more preferably 10 to 25min, and still more preferably 15 to 20min.
In the present invention, the polymerization reaction preferably includes a first polymerization reaction and a second polymerization reaction.
Finally, the reaction product obtained in the step and the inactivator are subjected to heat exchange, then the antioxidant is added for flash evaporation, and then the polyolefin elastomer is obtained after granulation.
The invention is a complete and detailed integral technical scheme, which better improves the continuity and stability of the production of the polyolefin elastomer, and the production process of the polyolefin elastomer specifically comprises the following steps:
a process for continuously preparing polyolefin elastomer features that the polymerizing temp is 60-250 deg.C and the pressure of ethylene is 1.0-15.0 MPa; the solvent is isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, an isomeric saturated alkane mixture and toluene; the comonomer is 1-butene, 1-hexene, 1-octene, 1-decene; the catalyst used is homogeneous catalyst such as Constrained Geometry Catalyst (CGC), bridged metallocene catalyst and non-metallocene catalyst, preferably dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, diphenylcarbanyl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride and [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphine ] titanium trichloride; the cocatalyst used is triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), perfluorophenylboron, triphenylcarbetetrakis (pentafluorophenyl) borate, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, N-dihexadecylammonium tetrakis (pentafluorophenyl) borate; reaction kettle residence time: 5-30 min.
Referring to FIG. 1, FIG. 1 is a schematic process flow diagram of a continuous polyolefin elastomer production process system provided by the present invention.
The invention provides a process system and a method for continuously producing polyolefin elastomer. The invention adopts two kettle type reactors, can be used independently or in series/parallel connection, and improves the problem that the polymer is stuck to the kettle by improving the stirring paddle, the mirror polishing of the kettle wall and other measures; more importantly, the invention adopts a jacket type special structure at the connecting part of the product and hot water, and the hot water flushes the product emerging from the inner pipe wall into a condensation kettle for stirring, granulating and devolatilizing. In addition, the refined raw material tank provided by the invention is provided with a differential pressure liquid level meter, and the liquid level meter is interlocked with the pump, so that automatic liquid supplement can be realized.
The invention firstly greatly improves the problem that the polymer is stuck to the kettle by improving the measures of stirring paddles, mirror polishing of the kettle wall and the like; simultaneously, two kettle type reactors which can be used in series/parallel connection are adopted, so that the reaction operation is simpler and more convenient; on the other hand, because POE has the characteristics of high elasticity and good toughness, the devolatilization process is complex, and the energy consumption of the traditional devolatilization, granulation and molding processing system is high, so that continuous large-scale production is not easy to realize. The invention improves the jacket type special structure, uses hot water to wash the product emerging from the inner pipe wall into the condensation kettle, and greatly reduces the processing cost through stirring, granulating and devolatilizing. In addition, the process is improved, the computer automatic control monitoring operation is adopted, a differential pressure liquid level meter arranged in the refining raw material tank is interlocked with a pump, automatic liquid supplement is realized, and the labor cost is effectively reduced.
The industrial verification result shows that the process system and the method provided by the invention are adopted to continuously produce the polyolefin elastomer, and the polymerization activity is 5 multiplied by 10 7 -10 8 kg/(mol.h), the conversion rate of ethylene per pass is 50-57%, and the conversion rate of 1-octene is 15-25%; the weight average molecular weight of the polyolefin elastomer was 25.3X 10 4 -32×10 4 The molecular weight distribution is 2.7-5.6, the molar insertion rate of 1-octene is 11-15%; the content of VOCs in the POE product is 500ppm.
To further illustrate the present invention, the following will describe in detail a polyolefin elastomer production system and a production process thereof in conjunction with examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
As shown in fig. 1.
A raw material refining unit: ethylene (water content: 0.241ppm, oxygen content: 0.312 ppm), 1-octene (water content: 0.335ppm, oxygen content: 0.453 ppm), n-hexane (water content: 0.544ppm, oxygen content: 0.339 ppm), toluene (water content: 0.328ppm, oxygen content: 0.347 ppm).
Catalyst preparation: 1.0mmol/L of toluene solution of a main catalyst (dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tert-butylamino-titanium dichloride), and the feeding flow rate is 60mL/h; the toluene solution of cocatalyst (MAO) was 300mmol/L, and the feed rate was 60mL/h.
A reaction unit: the ethylene flow is 0.35kg/h, the 1-octene flow is 0.70kg/h, the normal hexane flow is 1.68kg/h, the temperature of the premixing kettle is set to be 40 ℃, and the stirring speed is 500r/min; single pot polymerization: the polymerization temperature is 140 ℃, the stirring speed is 500r/min, and the pressure in the kettle is 4.0MPa.
A product separation unit: adding an antioxidant (a normal hexane solution is 1.0g/L, the feeding flow is 60 mL/h) at an inlet of the flash evaporation kettle, wherein the flash evaporation temperature is 180 ℃, and the pressure is 5KPa, and removing ethylene, 1-octene, normal hexane and toluene; and (3) introducing the concentrated solution in the flash evaporation kettle into a condensation kettle, wherein the temperature of the condensation kettle is 90 ℃, introducing a product which is sprayed out from the inner pipe wall and washed by hot water into the condensation kettle, stirring and granulating, then overflowing into a product tank, and filtering particles in the product tank.
Polymerization Activity 5.1X 10 7 kg/(mol. H), a single pass ethylene conversion of 57%, a 1-octene conversion of 18%; the weight average molecular weight of the polyolefin elastomer was 25.3X 10 4 The molar insertion rate of 3.6,1-octene, molecular weight distribution, was 11.7%; the content of VOCs in the POE product is 500ppm.
Example 2
As shown in fig. 1.
A raw material refining unit: ethylene (water content: 0.547ppm, oxygen content: 0.475 ppm), 1-octene (water content: 0.397ppm, oxygen content: 0.478 ppm), isopar E (water content: 0.536ppm, oxygen content: 0.463 ppm), toluene (water content: 0.365ppm, oxygen content: 0.334 ppm).
Catalyst preparation: the main catalyst (diphenyl carbon bridge group-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride) is 0.5mmol/L in toluene, and the feeding flow is 60mL/h; the cocatalyst is a Modified Methylaluminoxane (MMAO) toluene solution 200mmol/L, and the feed flow is 60mL/h.
A reaction unit: the flow rate of ethylene is 0.35kg/h, the flow rate of 1-octene is 1.05kg/h, the flow rate of Isopar E is 2.18kg/h, the set temperature of the premixing kettle is 60 ℃, and the stirring speed is 500r/min; single pot polymerization: the polymerization temperature is 150 ℃, the stirring speed is 500r/min, and the pressure in the kettle is 4.5MPa.
A product separation unit: adding an antioxidant (Isopar E solution is 1.0g/L, the feeding flow is 60 mL/h) at an inlet of the flash evaporation kettle, wherein the flash evaporation temperature is 200 ℃, the pressure is 3KPa, and removing ethylene, 1-octene, isopar E and toluene; and (3) introducing the concentrated solution in the flash evaporation kettle into a condensation kettle, controlling the temperature of the condensation kettle to be 90 ℃, introducing a product which is sprayed out from the inner pipe wall and is washed by hot water into the condensation kettle, stirring and granulating, then overflowing into a product tank, and filtering particles in the product tank.
Polymerization Activity 7.3X 10 7 kg/(mol. H), the per pass ethylene conversion is 62%, and the 1-octene conversion is 13%; the weight average molecular weight of the polyolefin elastomer was 27.5X 10 4 The molecular weight distribution was 3.7, and the molar insertion rate of 1-octene was 12.3%; the content of VOCs in the POE product is 500ppm.
Example 3
As shown in fig. 1.
A raw material refining unit: ethylene (water content: 0.247ppm, oxygen content: 0.428 ppm), 1-octene (water content: 0.359ppm, oxygen content: 0.439 ppm), isopentane (water content: 0.445ppm, oxygen content: 0.564 ppm), toluene (water content: 0.389ppm, oxygen content: 0.574 ppm).
Catalyst preparation: the toluene solution of the main catalyst ([ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenone ] titanium trichloride) is 1.5mmol/L, and the feeding flow is 60mL/h; the cocatalyst was triphenylcarbenium tetrakis (pentafluorophenyl) boron compound 3.0mmol/L, methylaluminoxane (MAO) in toluene 300mmol/L, and the feed rate was 60mL/h.
A reaction unit: the flow rate of ethylene is 0.35kg/h, the flow rate of 1-octene is 1.4kg/h, the flow rate of isopentane is 1.91kg/h, the set temperature of the premixing kettle is 50 ℃, and the stirring speed is 500r/min; two-pot polymerization: the polymerization temperature is 140 ℃, the stirring speed is 500r/min, and the pressure in the kettle is 4.0MPa.
A product separation unit: adding an antioxidant (isopentane solution is 1.0g/L, the feeding flow is 60 mL/h) at an inlet of the flash evaporation kettle, wherein the flash evaporation temperature is 180 ℃, and the pressure is 5KPa, and removing ethylene, 1-octene, isopentane and toluene; and (3) introducing the concentrated solution in the flash evaporation kettle into a condensation kettle, controlling the temperature of the condensation kettle to be 90 ℃, introducing a product which is sprayed out from the inner pipe wall and is washed by hot water into the condensation kettle, stirring and granulating, then overflowing into a product tank, and filtering particles in the product tank.
Polymerization Activity 9.2X 10 7 kg/(mol. H), the per pass ethylene conversion is 63%, and the 1-octene conversion is 12%; the weight average molecular weight of the polyolefin elastomer was 28.6X 10 4 The molar insertion rate of 4.1, 1-octene in the molecular weight distribution is 13.1%; the content of VOCs in the POE product is 500ppm.
The present invention is described in detail above with respect to a process system and method for the continuous production of polyolefin elastomers, and the principles and embodiments of the present invention are described herein using specific examples, which are included to assist in understanding the method and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A system for producing a polyolefin elastomer, comprising:
a first reaction kettle;
the second reaction kettle is connected with the first reaction kettle in series or in parallel;
the first reaction kettle and the second reaction kettle are provided with three-blade flat push paddles and three-blade inclined-blade turbine paddles;
the heat exchanger is connected with the second reaction kettle;
a flash tank connected to the heat exchanger;
a condensation kettle connected with the flash evaporation kettle;
a product tank connected to the coagulum kettle.
2. The production system according to claim 1, wherein the flash tank is connected to the coagulation tank by a jacket-type pipe;
the jacket type pipeline comprises a product inner pipe and a circulating hot water outer pipe;
one end of the product inner pipe is communicated with the flash evaporation kettle, and one end close to the condensation kettle is sealed;
the tube wall of the product inner tube is provided with a plurality of holes;
one end of the circulating hot water outer pipe is communicated with the condensation kettle.
3. The production system of claim 2, wherein the product tank has a multi-layer filtration device;
the bottom of the product tank is connected with the circulating hot water outer pipe;
the inner wall of the reaction kettle is a reaction kettle with a mirror polished surface;
one or more of a pressure gauge, a safety valve, a pressure sensor and a temperature probe are arranged on the reaction kettle;
the three-blade inclined blade turbine paddle comprises three-blade 45-degree inclined blade turbine paddles.
4. The production system of claim 1, further comprising a premix kettle;
the premixing kettle is connected with the first reaction kettle;
the first reaction kettle and the second reaction kettle are used independently or in series/parallel connection;
the production system further comprises a raw material refining unit;
the raw material refining unit comprises one or more of a deoxygenation tower, a dehydration tower, a desulfurization tower, a dechlorination tower and a decarbonylation tower.
5. The production system of claim 4, further comprising a feedstock unit;
the raw material unit comprises an ethylene raw material tank, a comonomer raw material tank, a solvent tank and a toluene tank;
the ethylene raw material tank is connected with the premixing kettle through a first raw material refining unit in the raw material refining units;
the comonomer raw material tank is connected with the premixing kettle through a second raw material refining unit in the raw material refining units;
the solvent tank is connected with the premixing kettle through a third raw material refining unit in the raw material refining unit.
6. The production system of claim 5, further comprising a main catalyst tank, a main catalyst configuration tank, a cocatalyst tank, and a cocatalyst configuration tank;
the main catalyst tank is respectively connected with the first reaction kettle and the second reaction kettle;
the cocatalyst tank is respectively connected with the first reaction kettle and the second reaction kettle;
the main catalyst configuration tank is connected with the main catalyst tank;
the cocatalyst configuration tank is connected with the cocatalyst tank;
and the toluene tank is respectively connected with the main catalyst configuration tank and the cocatalyst configuration tank through a fourth raw material refining unit in the raw material refining unit.
7. The production system of claim 1, further comprising a deactivator tank and an antioxidant tank;
the inactivator tank is connected to the production system through a connecting pipeline between the second reaction kettle and the heat exchanger;
the antioxidant tank is connected to a production system through a connecting pipeline between the heat exchanger and the flash evaporation kettle;
the condensation kettle comprises a stirring granulation condensation kettle;
the condensate is connected to the product tank by overflow.
8. A process for producing a polyolefin elastomer, comprising the steps of:
1) Premixing ethylene, comonomer and solvent, and then adding a main catalyst and a cocatalyst to carry out polymerization reaction to obtain a reaction product;
2) And (3) carrying out heat exchange on the reaction product obtained in the step and the inactivating agent, adding the antioxidant for flash evaporation, and then granulating to obtain the polyolefin elastomer.
9. The production process of claim 8, wherein the solvent comprises one or more of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, mixtures of isomeric saturated alkanes and toluene;
the comonomer comprises one or more of 1-butene, 1-hexene, 1-octene and 1-decene;
the catalyst comprises one or more of a constrained geometry catalyst, a bridged metallocene catalyst, and a non-metallocene catalyst;
the cocatalyst comprises one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dihexadecylphenylammonium tetrakis (pentafluorophenyl) borate;
the production process is a production process for continuously producing the polyolefin elastomer.
10. The production process according to claim 8, wherein the pressure of ethylene is 1.0 to 15.0MPa;
the catalyst specifically comprises one or more of dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-titanium dichloride, dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-dimethyl titanium, diphenyl carbon bridging group-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride and [ N- (3, 5-di-tert-butyl salicylidene) -2-diphenyl phosphorus phenyl imine ] titanium trichloride;
the temperature of the polymerization reaction is 60-250 ℃;
the time of the polymerization reaction is 5-30 min;
the polymerization reaction includes a first polymerization reaction and a second polymerization reaction.
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