CN109320639B - Alkoxy magnesium carrier and polyethylene catalyst component prepared from same - Google Patents
Alkoxy magnesium carrier and polyethylene catalyst component prepared from same Download PDFInfo
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- CN109320639B CN109320639B CN201811066711.3A CN201811066711A CN109320639B CN 109320639 B CN109320639 B CN 109320639B CN 201811066711 A CN201811066711 A CN 201811066711A CN 109320639 B CN109320639 B CN 109320639B
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- -1 Alkoxy magnesium Chemical compound 0.000 title claims abstract description 115
- 239000011777 magnesium Substances 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 52
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 36
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- IZMHKHHRLNWLMK-UHFFFAOYSA-M chloridoaluminium Chemical compound Cl[Al] IZMHKHHRLNWLMK-UHFFFAOYSA-M 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 239000011949 solid catalyst Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 206010011416 Croup infectious Diseases 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses an alkoxy magnesium carrier and a polyethylene catalyst component prepared by the same. The magnesium alkoxide support is obtained by spray drying a suspension of a magnesium alkoxide compound in the form of a gel dispersion and a carboxylated magnesium alkoxide compound in a solution state. Contacting an alkoxy magnesium carrier with titanium tetrachloride in an inert medium at a temperature of less than or equal to 50 ℃; gradually heating to 100 ℃ and 130 ℃, and carrying out contact reaction at the temperature; separating and washing the product with inert medium to obtain solid microsphere particles, namely the polyethylene catalyst component. A catalyst system for slurry polymerization of ethylene is obtained by reacting a polyethylene catalyst with an organoaluminum compound. The polyethylene catalyst obtained by the invention has good particle shape, and when the catalyst is used for ethylene polymerization, the resin powder has good particle shape, higher bulk density and obviously reduced fine powder content.
Description
Technical Field
The invention relates to an alkoxy magnesium carrier and a preparation method and application of a polyethylene catalyst component prepared by the alkoxy magnesium carrier, and belongs to the technical field of polyolefin catalysts.
Background
In recent 40 years, the preparation technology of polyolefin catalysts has been greatly developed, a batch of high-efficiency polyethylene catalysts are developed, the development work of high-performance polyethylene products is powerfully supported, and the consumption cost of the catalysts in the polyethylene products is reduced. The polymerization catalyst used in the slurry process polyethylene process is mainly divided into magnesium chloride-based and magnesium alkoxide-based catalysts according to the source of precursor magnesium. The preparation route of the magnesium chloride-based catalyst is generally that magnesium chloride is dissolved by adopting Lewis base solution, and precipitated under the action of titanium-containing compound to form catalyst precursor, and the technical scheme of the catalyst is disclosed in patent documents such as CN201510716358.9, CN201510717138.8, CN201510684825.4, CN201410273530.3, CN201210397456.7, CN201110270295.0, CN201110197236.5, CN98118334.4 and the like. The catalyst generally has the advantages of higher polymerization activity, concentrated particle size distribution, wider particle size adjusting range and the like, but generally has poorer hydrogen regulation sensitivity and lower polymerization activity under high hydrogen condition. The preparation technical route of the magnesium alkoxy group catalyst is mainly divided into two types, one type is that alkyl magnesium is prepared into particles, and then the alkyl magnesium particles react with a titanium compound in an inert solvent to form a catalyst precursor; the other is to dissolve the magnesium alkoxide and the titanium alkoxide to form a solution containing the magnesium alkoxide and the titanium alkoxide, and precipitate out under the action of a chlorinating agent/alkyl aluminum to form a catalyst precursor. Technical schemes of the catalyst are disclosed in patent documents such as US4859749A, US5292837A, US5648309, US7649061, US7759445, WO2011060954, WO0138405, CN200580025162, CN03819076, CN200580025162, CN200680004879, CN200980122271, CN201080035834, CN201180029854, US6335411, US6545106, CN96110046, CN201410725832, CN201410743733 and the like. The catalyst generally has the advantages of high activity, high hydrogen regulation sensitivity, tool performance and the like, and is particularly suitable for developing and producing bimodal resin products, but generally, the particle form is poor, the fluidity of resin powder is poor, the bulk density of the resin powder still needs to be further improved, the content of fine powder is high, the production load is improved due to the defects, and the blockage of a discharge pipeline is easily caused.
In view of the importance of catalyst particle morphology control, there is a need to develop an alkoxymagnesium-based slurry polyethylene catalyst having improved particle morphology while meeting production requirements in terms of catalyst activity and other properties.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prior alkoxy magnesium-based polyethylene catalyst has the defects of poor particle shape, higher fine powder content and lower powder bulk density.
In order to solve the above-mentioned problems, the present invention provides a magnesium alkoxide carrier obtained by spray-drying a suspension comprising a magnesium alkoxide compound in the form of a gel dispersion and a carboxylated magnesium alkoxide compound in a liquid solution.
The preparation process of the suspension in which the magnesium alkoxide compound in the form of a gel dispersion and the carboxylated magnesium alkoxide compound in a solution state are mixed is not particularly limited, and a suspension formed by physically mixing a suspension of the magnesium alkyl compound which has been dispersed in the form of a gel dispersion with a solution of the carboxylated magnesium alkyl compound may be used in a ratio of the magnesium alkyl compound to the carboxylated magnesium alkyl compound; it is also possible to add the desired amount of CO to the suspension of the magnesium alkyl compound already dispersed in the form of a gel dispersion2Carboxylating and dissolving part of the magnesium alkoxide compound to form magnesium alkoxide mixed in the form of gel dispersionA suspension of the compound and a solution of a carboxylated magnesium alkoxide compound. The method for preparing the gel dispersion of the magnesium alkoxide compound in suspension is not particularly limited, and any dispersion technique in the prior art may be employed. By way of example, commercially available large-particle magnesium alkoxide can be initially comminuted by grinding in an inert atmosphere to a particle size of 5 to 50 μm, then suspended and dispersed in a dispersion medium, and the magnesium alkoxide suspension can subsequently be dispersed in a high-speed disperser (e.g., Ultra-Turrax or Dispax, IKA-Maschinenbau Janke)&Kunkel GmbH) into a gel-like dispersion under high shear stress. So-called magnesium alkoxide gel-like dispersions are dispersions of magnesium alkoxide having an average particle size of less than 1 micron dispersed in a liquid medium, which dispersions are relatively stable, settle very slowly and are capable of producing the tyndall phenomenon. The magnesium alkoxide gel dispersion may be prepared by reacting magnesium powder with alcohol to prepare magnesium alkoxide particles autonomously, dispersing the particles in alcohol without drying, and passing the particles through a high-speed dispersing machine (e.g., Ultra-Turrax or Dispax, IKA-Maschinenbau Janke)&Kunkel GmbH) into a gel-like dispersion under high shear stress. Therefore, the step of grinding and crushing large-particle alkoxy magnesium is not needed, and the alkoxy magnesium with smaller particle size (such as less than 20 microns) can be prepared by optimizing the reaction conditions of magnesium powder and alcohol, so that the process is shortened, and the energy and the cost are saved.
The invention has no special limitation on the related spray drying process and the equipment and conditions used in the spray drying process, and the equipment and the method which can be used for spray forming and drying of organic phase materials in the prior art can be introduced into the invention for preparing the magnesium alkoxide microsphere particles. As examples, the spray drying apparatus may employ a pressure type spray dryer, a rotary type spray dryer or a two-fluid type spray dryer; the material drying process can be completed by a spray dryer at one time, or can be continuously dried after the spray dryer is connected with one or more drying devices in other forms (such as fluidized bed drying) in series, so that the drying is complete.
The chemical structural formula of the alkoxy magnesium compound is Mg (OR)1)(OR2)。
The chemical structural formula of the carboxylated alkoxy magnesium compound is Mg (OR)3)(OR4)·XCO2(ii) a Wherein R is1、R2、R3、R4All are alkyl groups containing 2-10 carbon atoms, and X is 1-2.
The molar ratio of the alkoxy magnesium compound to the carboxylated alkoxy magnesium compound is 1 (0.01-1), and more preferably 1 (0.05-0.3).
Preferably, R1, R2, R3 and R4 are all-C2H5。
Preferably, the average particle size of the alkoxy magnesium compound is 200-1200 μm, preferably 500-700 μm; in order to ensure the smooth forming and drying process of the small fog drops formed by the atomization of the suspension in the spray drying process, the solid content of the suspension is 5-80%, and preferably 10-30%. The liquid medium in the suspension is a polar liquid medium which does not chemically react with the magnesium alkoxide compound and the carboxylated magnesium alkoxide compound, and may be, for example, a liquid ether, a liquid ketone, a liquid alcohol, etc., preferably a liquid alcohol, and particularly preferably ethanol.
The invention also provides a polyethylene catalyst component, which is characterized by being obtained by a method comprising the following steps:
step a): contacting the alkoxy magnesium carrier with titanium tetrachloride in an inert medium at the temperature of less than or equal to 50 ℃;
step b): gradually heating the mixture obtained in the step a) to 100-130 ℃, and carrying out contact reaction at the temperature; the contact time at the lower temperature is more than 15 minutes and the contact time at the higher temperature should be not less than 15 minutes, preferably 0.5 to 5 hours.
Step c): separating the product obtained in the step b) and washing the product by using an inert medium to obtain solid microsphere particles, namely the polyethylene catalyst component.
Preferably, prior to said step a), the magnesium alkoxide support is further treated in an inert atmosphere at a temperature above 100 ℃ to decompose the carboxylated magnesium alkoxide compound in the solid microspheroidal particle to release CO2。
Preferably, the inert medium in step a) comprises aliphatic, cycloaliphatic and aromatic hydrocarbons, such as butane, pentane, hexane, heptane, cyclohexane, isooctane, benzene, toluene and xylene, it also being possible to use white spirit and hydrogenated diesel fractions from which oxygen, sulfur compounds and moisture have been removed.
Preferably, the molar ratio Cl/Ti in the polyethylene catalyst obtained in step c) is higher than 2.5, preferably at least 3, more preferably between 3 and 5; the Ti/Mg molar ratio is higher than 1, preferably in the range of 1.5 to 4, more preferably in the range of 1.75 to 2.75; the particle size of the polyethylene catalyst is 5 to 20 μm, preferably 7 to 15 μm.
Preferably, the above step further comprises step d): further contacting said solid microspheroidal particles obtained in step c) with an alkylaluminium halide at a temperature of 0-150 ℃, preferably 30-100 ℃ for 0.5-5 hours to bring some of the titanium atoms from the oxidized state Ti4+Reduced to Ti in oxidized state3+(ii) a The alkyl aluminum halide has a chemical structural formula of R3 2The chemical structural formula of dialkyl aluminum monochloride or dialkyl aluminum monochloride of AlCl is R3 3Al2Cl3Wherein R is3Are identical or different alkyl radicals having from 1 to 16 carbon atoms; the molar ratio Al/Ti in the polyethylene catalyst obtained in step d) is 0.05-1, preferably 0.1-0.5, and the molar ratio Cl/Ti is not less than 3, preferably higher than 3.5. The Cl/Ti molar ratio is increased with respect to the Cl/Ti molar ratio of the solid before step d).
More preferably, the alkylaluminum halide is diethylaluminum monochloride or ethylaluminum sesquichloride.
The invention also provides a catalyst system for slurry polymerization of ethylene, which is characterized by being obtained by reacting the polyethylene catalyst component and the organic aluminum compound in a mass ratio of 1: 0.1-20; the organic aluminum compound is trialkyl aluminum compound or the mixture of trialkyl aluminum compound and alkyl aluminum halide.
Preferably, the trialkylaluminum compound is Trimethylaluminum (TMA), Triethylaluminum (TEAL), Triisobutylaluminum (TIBA), tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum or triisopentadienylaluminum.
Preferably, the alkyl aluminum halide is an alkyl aluminum chloride.
More preferably, the alkylaluminum chlorides are diethylaluminum chloride (DEAC), diisobutylaluminum chloride, Al-sesquichloride and dimethylaluminum chloride (DMAC).
When the above catalyst system is used, it is prepolymerized with an alpha-olefin and the prepolymerized catalyst system is subsequently used in the main polymerization.
Preferably, the alpha-olefin is linear C2-C10-an olefin.
More preferably, the alpha-olefin is ethylene or propylene.
The polyethylene catalyst and the polyethylene powder prepared by the polyethylene catalyst have good particle morphology, good fluidity and lower fine powder content.
The catalyst system of the present invention is particularly suitable for slurry polymerization processes. In practice, average particle sizes such as less than 20 μm, preferably from 7 to 15 μm, are particularly suitable for slurry polymerizations in an inert medium, which can be carried out continuously in stirred reactors or loop reactors. In a preferred embodiment, the ethylene polymerization process is carried out in two or more serially connected loop reactors or stirred reactors, producing polymers with different molecular weights and/or different compositions in each reactor, thereby showing a broad molecular weight distribution and/or monomer composition as a whole.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
a) Preparation of magnesium ethoxide microspheroidal particles
57g (0.5mol) Mg (OC)2H5)2The solid powder and 200mL of ethanol were placed in a 500mL milling jar and milled for 5 hours using a PM-400 ball mill from Lechly, Germany to obtain Mg (OC) having an average particle size of 5.5 μm2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)2100mL of the suspension of (2) is transferred to N2To a replacement four-necked reaction flask, 50mL of ethanol was added and the volume of the mixture was increasedThe fast disperser (Krupp Superaton (TM) type S200) was treated at 60 ℃ for 20 hours, forming a gel-like dispersion.
To the gel dispersion obtained above, 0.22g of dry ice (0.005mol) was added and stirred to react for 1 hour to obtain a gel-like dispersion suspension of ethoxymagnesium containing a carboxylated ethoxymagnesium solution.
And (3) carrying out spray drying (Buchi B290) on the obtained gel dispersion suspension to obtain solid microsphere particles, wherein the spraying conditions are that the inlet temperature is 200 ℃, the outlet temperature is 163 ℃, the opening degree of a feed pump is 25%, and the atomizing gas flow is 742L/h. The solid microspheroidal particle D50 was 9.8 μm.
The solid microspherical particles obtained above were charged into a quartz tube under a nitrogen atmosphere, heated to 130 ℃ in a nitrogen flow, and kept heated for 10 hours to allow CO to be present2Is effectively removed. The resulting solid microspheroidal particle D50 was 9.6 μm.
b) Preparation of solid catalyst component a:
weighing 10g of the magnesium ethoxide microspheroidal particles prepared in step a), adding into the solution2200mL of toluene is added into the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to be 200r/min, and the oil bath temperature is reduced to 5 ℃. 19.6mL of TiCl were slowly added dropwise4(Ti/Mg ═ 2), after completion of the dropwise addition, maintained at 5 ℃ for 30min, then slowly warmed to 110 ℃ and maintained at 110 ℃ for reaction for 2hr, then left to stand and filtered and washed twice with toluene, in an amount of 200mL per toluene, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly added dropwise with stirring while starting, and reacted at 80 ℃ for 30min, then left to stand and washed three times with hexane, in an amount of 200mL per hexane, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component. The solid catalyst component D50 was 10.2 μm.
c) Polymerization of ethylene in suspension:
1L of hexane, 5mmol of triethylaluminum and a certain amount of catalyst are added into a 2L stainless steel stirring kettle, then the temperature is increased to 80 ℃, 0.28MPa of hydrogen is added at a time, then the total pressure of the system is maintained at 0.73MPa by using ethylene for polymerization reaction, after 2 hours of reaction, the addition of ethylene is stopped, the temperature is reduced, the pressure is relieved, polyethylene powder is weighed, the activity of the catalyst is calculated, and the bulk density and the melt index under the load of 2.16kg of the polyethylene powder are tested, and the results are shown in Table 1.
Example 2
a) Preparation of magnesium ethoxide microspheroidal particles
57g (0.5mol) Mg (OC)2H5)2The solid powder and 200mL of ethanol were placed in a 500mL milling jar and milled for 5 hours using a PM-400 ball mill from Lechly, Germany to obtain Mg (OC) having an average particle size of 5.5 μm2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)2100mL of the suspension of (2) is transferred to N2To the replaced four-necked reaction flask, 50mL of ethanol was added and treated with a high-speed disperser (Krupp Superaton TM S200) at 60 ℃ for 20 hours to form a gel-like dispersion.
To the gel dispersion obtained above was added 0.33g of dry ice (0.0075mol), and the reaction was stirred for 1 hour to obtain a gel-like dispersion suspension of ethoxymagnesium containing a carboxylated ethoxymagnesium solution.
And (3) carrying out spray drying (Buchi B290) on the obtained gel dispersion suspension to obtain solid microsphere particles, wherein the spraying conditions are that the inlet temperature is 210 ℃, the outlet temperature is 170 ℃, the opening degree of a feed pump is 25%, and the atomizing gas flow is 742L/h. The solid microspheroidal particle D50 was 8.9 μm.
The solid microspherical particles obtained above were charged into a quartz tube under a nitrogen atmosphere, heated to 130 ℃ in a nitrogen flow, and kept heated for 10 hours to allow CO to be present2Is effectively removed. The resulting solid microspheroidal particle D50 was 8.8 μm.
b) Preparation of solid catalyst component a:
as in example 1, the solid catalyst component D50 was 9.1 μm.
c) Polymerization of ethylene in suspension:
the same as in example 1.
Example 3
a) Preparation of magnesium ethoxide microspheroidal particles
Same as example 1
b) Preparation of solid catalyst component a:
weighing 10g of the magnesium ethoxide microspheroidal particles prepared in step a), adding into the solution2200mL of toluene is added into the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to be 200r/min, and the oil bath temperature is reduced to 0 ℃. 24.5mL of TiCl were slowly added dropwise4(Ti/Mg ═ 2.5), after completion of the dropwise addition, maintained at 0 ℃ for 30min, then slowly warmed to 115 ℃ and maintained at 115 ℃ for 2hr of reaction, then left to stand, filtered and washed twice with toluene, in an amount of 200mL per toluene, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly added dropwise with stirring, and reacted at 80 ℃ for 30min, then left to stand and washed three times with hexane, in an amount of 200mL per hexane, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component. The solid catalyst component D50 was 10.3 μm
c) Polymerization of ethylene in suspension:
the same as in example 1.
Comparative example 1
a) Preparation of magnesium ethoxy granules
40g (0.5mol) of Mg (OC)2H5)2The solid powder and 200mL of toluene were charged into a 500mL milling jar and milled for 5 hours using a PM-400 ball mill from Lechly, Germany to obtain Mg (OC) having an average particle size of 5.5 μm2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)250mL of the suspension of (2) is transferred to N2To the replaced four-necked reaction flask, 150mL of toluene was added and treated with a high-speed disperser (Krupp Superaton TM S200) at 40 ℃ for 30 hours to form a gel-like dispersion.
b) Preparation of solid catalyst component a:
transferring the gel-like dispersion obtained in a) to a column via N2In the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to 200r/min, and the oil bath temperature is reduced to 5 ℃. Slowly adding 24.5mL TiCl4(Ti/Mg is 2.5) dropwise, maintaining at 5 deg.C for 30min after dropwise addition, slowly heating to 110 deg.C, maintaining at 110 deg.C for reaction for 2hr, standing, filtering, and mixing with the filtrateToluene was washed twice with 200mL of toluene each time, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly dropped with stirring, and reacted at 80 ℃ for 30min, then allowed to stand, and washed three times with 200mL of hexane each time, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component.
c) Polymerization of ethylene in suspension:
the same as in example 1.
TABLE 1
As can be seen from Table 1, the solid polyethylene catalyst component obtained by the present invention has good particle morphology, resin powder used in ethylene polymerization has good particle morphology, higher bulk density, and significantly reduced fine powder content.
Claims (9)
1. An alkoxy magnesium carrier, which is characterized in that the alkoxy magnesium carrier is obtained by spray drying a suspension of an alkoxy magnesium compound in a gel dispersion state and a carboxylated alkoxy magnesium compound in a solution state;
the chemical structural formula of the alkoxy magnesium compound is Mg (OR)1)(OR2)；
The chemical structural formula of the carboxylated alkoxy magnesium compound is Mg (OR)3)(OR4)·XCO2(ii) a Wherein R is1、R2、R3、R4Are alkyl groups containing 2-10 carbon atoms, and X is 1-2; r1, R2, R3 and R4 are all-C2H5；
The molar ratio of the alkoxy magnesium compound to the carboxylated alkoxy magnesium compound is 1 (0.01-1).
2. The magnesium alkoxide support according to claim 1, wherein the magnesium alkoxide compound has an average particle size of 200-1200 μm; the solids content of the suspension is 5-80%.
3. A polyethylene catalyst component obtainable by a process comprising the steps of:
step a): contacting the magnesium alkoxide support of claim 1 or 2 with titanium tetrachloride in an inert medium at a temperature of 50 ℃ or less;
step b): gradually heating the mixture obtained in the step a) to 100-130 ℃, and carrying out contact reaction at the temperature;
step c): separating the product obtained in the step b) and washing the product by using an inert medium to obtain solid microsphere particles, namely the polyethylene catalyst component.
4. The polyethylene catalyst component according to claim 3 wherein the magnesium alkoxide support is further treated in an inert atmosphere at a temperature above 100 ℃ prior to step a).
5. The polyethylene catalyst component of claim 3 wherein the inert medium in step a) comprises aliphatic, cycloaliphatic and aromatic hydrocarbons.
6. The polyethylene catalyst component according to claim 3 wherein the molar ratio Cl/Ti in the polyethylene catalyst obtained in step c) is higher than 2.5; the Ti/Mg molar ratio is higher than 1; the particle size of the polyethylene catalyst is 5-20 μm.
7. The polyethylene catalyst component according to claim 3, further comprising step d): further contacting the solid microspheroidal particles obtained in step c) with an alkyl aluminium halide at 0-150 ℃ for 0.5-5 hours; the alkyl aluminum halide has a chemical structural formula of R3 2The chemical structural formula of dialkyl aluminum monochloride or dialkyl aluminum monochloride of AlCl is R3 3Al2Cl3Wherein R is3Are identical or different alkyl radicals having from 1 to 16 carbon atoms; the molar ratio of Al/Ti in the polyethylene catalytic compound obtained in the step d) is 0.05-1, and the molar ratio of Cl/Ti is not less than 3.
8. The polyethylene catalyst component of claim 7 wherein the alkylaluminum halide is diethylaluminum monochloride or ethylaluminum sesquichloride.
9. A catalyst system for slurry polymerization of ethylene, obtained by reacting the polyethylene catalyst component according to any one of claims 3 to 8 with an organoaluminum compound in a mass ratio of 1: 0.1 to 20; the organic aluminum compound is trialkyl aluminum compound or a mixture of the trialkyl aluminum compound and alkyl aluminum halide; the catalyst system is used by prepolymerising it with an alpha-olefin and subsequently using the prepolymerised catalyst system in the main polymerisation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540679A (en) * | 1984-03-23 | 1985-09-10 | Amoco Corporation | Magnesium hydrocarbyl carbonate supports |
| CN86105015A (en) * | 1985-08-28 | 1987-02-25 | 国际壳牌研究有限公司 | Preparation method of magnesium alcohol spherical particles |
| CN101831015A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
| CN102482371A (en) * | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst Components for Olefin Polymerization |
| CN105482004A (en) * | 2015-12-04 | 2016-04-13 | 淄博新塑化工有限公司 | Composite catalyst for preparation of broad peak / bimodal distribution high density polyethylene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540679A (en) * | 1984-03-23 | 1985-09-10 | Amoco Corporation | Magnesium hydrocarbyl carbonate supports |
| CN86105015A (en) * | 1985-08-28 | 1987-02-25 | 国际壳牌研究有限公司 | Preparation method of magnesium alcohol spherical particles |
| CN101831015A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
| CN102482371A (en) * | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst Components for Olefin Polymerization |
| CN105482004A (en) * | 2015-12-04 | 2016-04-13 | 淄博新塑化工有限公司 | Composite catalyst for preparation of broad peak / bimodal distribution high density polyethylene |
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