CN116023540A - Preparation method of polyolefin catalyst carrier, catalyst and application - Google Patents
Preparation method of polyolefin catalyst carrier, catalyst and application Download PDFInfo
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- CN116023540A CN116023540A CN202111252267.6A CN202111252267A CN116023540A CN 116023540 A CN116023540 A CN 116023540A CN 202111252267 A CN202111252267 A CN 202111252267A CN 116023540 A CN116023540 A CN 116023540A
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- catalyst
- magnesium
- carrier
- alcohol
- reaction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000011777 magnesium Substances 0.000 claims abstract description 57
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 54
- -1 alkoxy magnesium Chemical compound 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000012686 silicon precursor Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000002140 halogenating effect Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000012442 inert solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 45
- 239000010936 titanium Substances 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 0.000 claims description 10
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003900 succinic acid esters Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- AVBCBOQFOQZNFK-UHFFFAOYSA-N dipropoxy(dipropyl)silane Chemical compound CCCO[Si](CCC)(CCC)OCCC AVBCBOQFOQZNFK-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000011246 composite particle Substances 0.000 abstract description 8
- 241001391944 Commicarpus scandens Species 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 38
- 238000010992 reflux Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- TXFBTGWUZRBEHR-UHFFFAOYSA-J tetrachloroiron Chemical compound Cl[Fe](Cl)(Cl)Cl TXFBTGWUZRBEHR-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of a polyolefin catalyst carrier, the carrier, a catalyst and application. The method comprises the following steps: 1) Adding a halogenating agent and mixed alcohol into an inert solvent under inert atmosphere, stirring for reaction, and cooling to-15-10 ℃; 2) Adding magnesium powder, heating to 60-90 ℃, reacting, filtering, washing and drying to obtain alkoxy magnesium particles; 3) Adding a silicon precursor and a metal precursor into an oxygen donor organic solvent, uniformly mixing, adding the alkoxy magnesium particles obtained in the step 2), reacting, filtering, washing and drying to obtain the polyolefin catalyst carrier. The invention improves the mechanical strength of the carrier by preparing the gel-bonding reinforced alkoxy magnesium composite particles, and the carrier is used for preparing the catalyst for olefin polymerization, and the obtained polymer particles are not easy to break, have low content of fine powder and high bulk density.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a polyolefin catalyst carrier, the carrier, a catalyst and application.
Background
Polyethylene, which is the most widely used synthetic resin in the world, is widely used in agriculture, construction, fishery, petrochemical industry, medical treatment, household appliances, automobiles, etc. The catalyst technology is a key core technology of polyethylene synthetic resin, and is also a key breakthrough point for realizing high performance of the polyethylene resin. With the continuous development of polyolefin catalyst technology, the preparation methods of polyolefin catalysts currently include various methods such as loading type, post-treatment type, dissolution precipitation type, spray drying type, and the like. In addition to the high activity of the catalyst required in many polyolefin process production processes, it is also important to control the morphology, particle size and particle size distribution of the catalyst, especially the fines produced during the polymerization process, which are detrimental to the elevation of the plant load and the long-period stable operation at too high a level.
The magnesium alkoxide supported catalyst using magnesium alkoxide as a carrier is an important catalyst for olefin polymerization by virtue of its advantages such as good particle shape and excellent hydrogen regulation performance. In the preparation process of the alkoxy magnesium supported catalyst, the catalyst can well replicate the particle morphology, particle size distribution and the like of the alkoxy magnesium particles.
In the prior art, chinese patent CN 101906017a describes a method for preparing magnesium alkoxide from magnesium powder, mixed alcohol and halogen.
Chinese patent CN107936154a describes a method for preparing a polyolefin catalyst support of controlled size and excellent particle morphology by introducing a surfactant.
However, it is known that the magnesium alkoxide particles are formed by randomly stacking platelets of small molecular magnesium alkoxide, and the interaction force inside the particles is weak, and these causes the magnesium alkoxide particles to have relatively poor mechanical strength, and the resulting catalyst has a high content of fine powder when ethylene polymerization is performed.
Therefore, the preparation of the catalyst with excellent crushing resistance, high bulk density and good particle morphology is a technical problem to be solved urgently at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a polyolefin catalyst carrier, the carrier, a catalyst and application. The mechanical strength of the carrier is improved by preparing the gel-bonding-enhanced alkoxy magnesium composite particles, and the carrier is used for preparing the catalyst for olefin polymerization, so that the obtained polymer particles are not easy to break, the content of fine powder is low, and the bulk density is high.
It is an object of the present invention to provide a process for the preparation of a polyolefin catalyst support.
The method comprises the following steps:
1) Adding a halogenating agent and mixed alcohol into an inert solvent under inert atmosphere, stirring for reaction, and cooling to-15-10 ℃;
2) Adding magnesium powder, heating to 60-90 ℃, reacting, filtering, washing and drying to obtain alkoxy magnesium particles;
3) Adding a silicon precursor and a metal precursor into an oxygen donor organic solvent, uniformly mixing, adding the alkoxy magnesium particles obtained in the step 2), reacting, filtering, washing and drying to obtain the polyolefin catalyst carrier.
In a preferred embodiment of the present invention,
in the step (1) of the process,
the inert atmosphere is a protective gas which does not participate in the reaction, preferably an inert gas and nitrogen, more preferably argon or nitrogen;
the inert solvent is at least one selected from benzene, toluene, xylene, hexane, heptane, octane, decane, white oil and paraffin; more preferably at least one from toluene, hexane, decane, heptane, white oil;
the halogenating agent is at least one of iodine simple substance, magnesium iodide, magnesium chloride and manganese chloride;
the mixed alcohol is at least one of a linear or branched monohydric alcohol or a polyhydric alcohol; preferably a mixed alcohol selected from the group consisting of C1-C10 alcohols, more preferably a mixed alcohol of ethanol and isooctanol, or a mixed alcohol of ethanol and butanol;
preferably, the molar content of isooctyl alcohol or butanol in the mixed alcohol is 1-20%.
In a preferred embodiment of the present invention,
in the step 1), the reaction time is 10-120 min.
In a preferred embodiment of the present invention,
in the step 2) of the process, the process is carried out,
the average grain diameter of the magnesium powder is 50-300 mu m;
the reaction time is 1-12 h.
In a preferred embodiment of the present invention,
the mol ratio of the halogenating agent to the magnesium powder is (0.002-0.1): 1;
the mol ratio of the mixed alcohol to the magnesium powder is (2-15): 1.
In a preferred embodiment of the present invention,
in the step 3) of the method,
the silicon precursor is at least one selected from silicon chloride, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane and dipropyldipropoxysilane;
the metal precursor is inorganic metal halide or organic metal alkoxide, preferably at least one of titanium tetrachloride, butyl titanate, isopropyl titanate, zirconium oxychloride, zirconium isopropoxide, propyl zirconate, tin chloride, iron tetrachloride and lanthanum chloride;
the oxygen donor organic solvent is an alcohol or ether solvent, preferably at least one selected from methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, diethyl ether, isopropyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, tetrahydrofuran and dioxane.
In a preferred embodiment of the present invention,
step 3), the reaction temperature is 50-160 ℃; the reaction time is 1-48 hours;
the molar ratio of the silicon precursor to magnesium is (0.01-2): 1, preferably (0.01-1): 1; more preferably (0.01-0.5): 1;
the molar ratio of the metal precursor to magnesium is (0.01-30): 1, preferably (0.1-20): 1;
the molar ratio of the oxygen donor organic solvent to magnesium is (10-300): 1, preferably (20-150): 1.
Wherein the mole number of magnesium refers to the mole number of magnesium in the alkoxy magnesium carrier particles.
It is a second object of the present invention to provide a polyolefin catalyst support produced by the method according to one of the objects of the present invention.
The carrier is granular, spherical, average grain size of 10-60 μm, grain size distribution of 0.6-1.4 and bulk density of 0.2-0.6 g/cm 3 。
It is a further object of the present invention to provide a Ziegler-Natta catalyst component for the polymerization of olefins.
A reaction product comprising the following components:
a) The second object of the present invention is a catalyst carrier;
b) A liquid titanium compound; the titanium compound has the general formula of Ti (OR) n X 4-n Wherein R is C 1 ～C 8 Hydrocarbon group, X is halogen atom, n is more than or equal to 0 and less than or equal to 4;
c) An internal electron donor compound.
The titanium compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、 Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、 Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl and Ti (OC) 2 H 5 ) 3 At least one of I;
the internal electron donor compound is at least one of esters, ethers, phenols, ketones, carboxylic acids and organic siloxane compounds; preferably at least one of esters, ethers and organosiloxanes; more preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, succinic acid ester, diethyl ether, butyl ether, tetrahydrofuran, tetramethoxysilane, tetraethoxysilane.
The preparation method of the Ziegler-Natta catalyst component can adopt the conventional preparation method of the traditional Ziegler-Natta catalyst component, and in the invention, the preparation method can preferably comprise the following steps:
the magnesium alkoxide particles are dispersed in a solvent of hexane and toluene and contacted with a titanium compound containing titanium and an internal electron donor, respectively, to obtain the Ziegler-Natta catalyst component for olefin.
The fourth object of the present invention is to provide a catalyst for olefin polymerization.
The catalyst comprises:
1) A catalyst component according to the third object of the present invention;
2) An organoaluminum compound;
the general formula of the organic aluminum compound is AlR m X 3-m Wherein R is hydrogen or C 1 ～C 20 And the alkyl group X is halogen atom, and m is more than 0 and less than or equal to 3.
The fifth object of the present invention is to provide a catalyst for olefin polymerization according to the fourth object of the present invention.
The olefin is preferably one or a mixture of ethylene, butene and hexene.
The invention adopts the following technical scheme:
a method for preparing a polyolefin catalyst support comprising the steps of:
1) Adding a halogenating agent and mixed alcohol into an inert solvent under inert atmosphere, stirring and reacting, and cooling to-15-10 ℃;
2) Adding magnesium powder in one or more times, heating to 60-90 ℃, reacting for 1-12 h, filtering and washing for 2-6 times, and drying the obtained solid to obtain alkoxy magnesium particles;
3) Adding a silicon precursor and a metal precursor into an alcohol or ether oxygen donor organic solvent, uniformly mixing, pouring alkoxy magnesium particles, reacting for 1-48 hours at 50-160 ℃, filtering, washing for 2-6 times, and drying the obtained solid to obtain gel bonding enhanced alkoxy magnesium composite particles.
According to the embodiment of the invention, the silicon precursor, the metal precursor and the oxygen donor organic solvent are subjected to sol-gel heterogeneous condensation reaction at high temperature, the formed oligomer can fully and effectively enter gaps inside alkoxy magnesium particles, the oligomer continues to undergo high-temperature reaction to be gelled and aged, the effect of adhesion enhancement is achieved, the composite material structure system is beneficial to improving the mechanical strength of the whole alkoxy magnesium particles, is more beneficial to improving the anti-crushing performance of an alkoxy magnesium supported catalyst, and reduces fine powder generated by ethylene polymerization.
According to an embodiment of the present invention, the mixed alcohol is a linear or straight monohydric alcohol or polyhydric alcohol, preferably a mixed alcohol of alcohols of C1 to C10, more preferably one of a mixed alcohol of ethanol and isooctanol, or a mixed alcohol of ethanol and butanol, wherein the molar content of isooctanol or butanol in the mixed alcohol is 1% to 20%.
According to an embodiment of the present invention, the halogenating agent is preferably at least one selected from elemental iodine, magnesium iodide, magnesium chloride, and manganese chloride.
In the preparation of the alkoxy magnesium particles, the average particle size of magnesium powder is 50-300 mu m; the shape of the magnesium powder is not particularly limited in the case of good reaction, and preferably spherical particles.
In the preparation of the alkoxy magnesium particles, magnesium powder can be added at one time or can be added in multiple times according to reaction conditions.
In the preparation of the alkoxy magnesium particles, the halogenating agent and the magnesium powder can be added into the reaction system independently or in the form of solution.
In the preparation of the alkoxy magnesium particles, the addition sequence and the reaction temperature of the reaction substances can be adjusted according to the product requirement; the reaction degree is judged according to the discharge amount of hydrogen.
In the preparation of the carrier, the form, the type and the stirring speed of the stirring paddle are not limited, and the stirring speed is realized by adjusting the form, the type and the stirring speed of the stirring paddle according to the requirements of products.
In the preparation of the carrier of the present invention, the reaction product may be washed with ethanol, mixed alcohol, and any one of organic solvents, and the manner and manner of washing are not limited.
The carrier of the invention can be used for storing the product in the form of dry powder after being dried, and can also be used for storing the product in the form of suspension slurry.
A catalyst component for the polymerization of olefins comprising the reaction product of:
a) A carrier (alkoxymagnesium carrier particles);
b) A liquid titanium compound; wherein the titanium compound has the general formula of Ti (OR) n X 4-n Wherein R is C 1 ～C 8 The alkyl, X is halogen atom, n is more than or equal to 0 and less than or equal to 4; the titanium compound is selected from TiCl 4 、TiBr 4 、TiI 4 、 Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、 Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl and Ti (OC) 2 H 5 ) 3 At least one of I, preferably TiCl 4 。
C) An internal electron donor compound.
According to an embodiment of the present invention, the internal electron donor compound is at least one selected from esters, ethers, phenols, ketones, carboxylic acids, and organosiloxanes; preferably at least one of esters, ethers and organosiloxanes; more preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, succinic acid ester, diethyl ether, butyl ether, tetrahydrofuran, tetramethoxysilane, tetraethoxysilane.
A catalyst for olefin polymerization, comprising:
1) The catalyst component described above;
2) An organoaluminum compound;
the general formula of the organic aluminum compound is AlR m X 3-m Wherein R is hydrogen or C 1 ～C 20 The hydrocarbon group X is halogen atom, 0 < m.ltoreq.3, and the organoaluminum compound may be selected from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、 AlH(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 、AlCl(CH 2 CH 3 ) 2 And AlCl 2 (CH 2 CH 3 ) At least one of them.
Preferably, the organoaluminum compound is selected from Al (CH) 2 CH 3 ) 3 And/or Al (i-Bu) 3 。
The invention has the following beneficial technical effects:
1. the mechanical strength of the alkoxy magnesium particles is improved by preparing the alkoxy magnesium composite particles with enhanced gel adhesion;
2. the alkoxy magnesium particles are used for preparing the catalyst for olefin polymerization, and the obtained polymer particles are not easy to break, have low content of fine powder and high bulk density;
3. the catalyst for olefin polymerization prepared by taking the alkoxy magnesium as a carrier can be suitable for different olefin polymerization processes.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In the following examples and comparative examples:
1. particle size and particle size distribution of the magnesium alkoxide support and catalyst: a Malvern Mastersizer TM 2000 laser particle sizer was used. Wherein span= (D90-D10)/D50.
2. Bulk density of polymer: measured by the weight of loose solids per unit volume. (GB/T1636).
3. The polymer fine powder content was sieved with a 200 mesh (75 μm) sieve to obtain 100g of powder, and the amount of the sieved polymer was W, whereby the content of the fine powder was W%.
The raw materials used in the examples are all commercially available products.
The invention will be further illustrated with reference to specific examples.
Example 1
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated.
(1) Fully replacing the reactor with high-purity nitrogen, adding 0.3g (1.1 mmol) of iodine and 120mL of mixed alcohol (ethanol and isooctanol, the molar ratio of ethanol to isooctanol is 2:0.05 (total mole number is 2.05), 30mL (0.28 mol) of toluene under the protection of nitrogen, stirring for 30min, and then cooling to 0 ℃;
(2) 6.3g (0.26 mol) of magnesium powder (average particle size 180 μm) was added, the temperature was raised to 75℃to carry out the reaction, the reaction was carried out at the reflux temperature for 4 hours, and the mixture was washed four times with absolute ethanol and hexane, and then separated and dried to obtain a white solid powder (alkoxymagnesium carrier) having excellent fluidity.
(3) 1g (6.6 mmol) of methyl orthosilicate, 14g (73.8 mmol) of titanium tetrachloride and 100mL (2.5 mol) of methanol are weighed in a reaction flask under anhydrous condition and uniformly mixed, then 4g of alkoxy magnesium particles (about 35mmol containing Mg) are poured, the mixture is transferred to a reaction kettle and transferred to an oven with the temperature of 80 ℃ for heterogeneous condensation reaction for 12 hours, and then the catalyst carrier with enhanced gel adhesion is obtained after washing four times by absolute ethyl alcohol and hexane, separation and drying.
(4) Into 300mL of a stirred 5-port reaction kettle with nitrogen fully replaced, 4g of the prepared carrier obtained in the step (3) and 40mL of toluene are added, the temperature is reduced to minus 15 ℃, and 20mL of TiCl is slowly added dropwise under stirring 4 When in use, the time is 1h; heating to 100deg.C, keeping the temperature for 2h, standing for settling, decanting supernatant, and adding 30mL TiCl again to the obtained solid 4 And 3mL of tetraethoxysilane, keeping the temperature for 1h, standing and settling, filtering the clear liquid under pressure, washing with 100mL of hexane for multiple times at 60 ℃ and drying to obtain the solid catalyst with good fluidity.
After the stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 2.0mL of triethylaluminum with the concentration of 1M are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, the pressure in the kettle reaches 0.28MPa by introducing hydrogen, the total pressure in the kettle reaches 0.73MPa by introducing ethylene, and the polymerization is carried out for 2 hours at 80 ℃.
Example 2
The same procedure as in example 1 was followed, except that: and respectively adjusting the silicon precursor and the metal precursor which are added into the reaction system into silicon chloride and butyl titanate with the same mole number.
Example 3
The same procedure as in example 1 was followed, except that: the addition amounts of the silicon precursor methyl orthosilicate and the metal precursor titanium tetrachloride added to the reaction system were adjusted to 0.5g and 7g, respectively.
Example 4
The same procedure as in example 1 was followed, except that: the oxygen donor solvent added to the reaction system was adjusted from methanol to diethyl ether having the same volume.
Example 5
The same procedure as in example 1 was followed, except that: the amount of methanol as an oxygen donor solvent added to the reaction system was adjusted to 200mL.
Example 6
The same procedure as in example 1 was followed, except that the reaction temperature and time in step (3) were adjusted to 60℃and 2 hours, respectively.
Example 7
The same procedure as in example 1 is followed, except for the preparation of the magnesium alkoxide, which is as follows:
in the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, adding 0.13g (0.5 mmol) of iodine and 200mL of mixed alcohol (ethanol and isooctanol, the addition amount of isooctanol is 2 mL) into 30mL (0.28 mmol) of toluene, stirring for 10min, and then cooling to-15 ℃;
(2) 6.3g (0.26 mol) of magnesium powder (particle size of 70 μm respectively) is added, the temperature is raised to 60 ℃ for reaction, and the reflux temperature is maintained for reaction for 4 hours; standing for sedimentation, press-filtering clear liquid, washing with absolute ethyl alcohol and hexane for four times, separating, and drying to obtain white solid powder (alkoxy magnesium carrier particles) with good fluidity.
Example 8
The same procedure as in example 1 is followed, except for the preparation of the magnesium alkoxide, which is as follows:
with stirringIn the reactor of the reactor, a reflux condensing pipe is arranged, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be conveniently observed 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, adding 0.66g (2.4 mmol) of iodine and 50mL of mixed alcohol (ethanol and isooctanol, the addition amount of isooctanol is 10 mL) into 30mL (0.28 mmol) of toluene, stirring for 90min, and cooling to 10 ℃;
(2) 6.3g (0.26 mol) of magnesium powder (particle size 300 μm) is added, the temperature is raised to 90 ℃ for reaction, and the reflux temperature is maintained for reaction for 8 hours; standing for sedimentation, press-filtering clear liquid, washing with anhydrous ethanol and hexane for four times, separating, and drying to obtain white solid powder (alkoxy magnesium carrier) with good fluidity
Example 9
The same procedure as in example 1 was followed except for the preparation stage of the magnesium alkoxide composite particles, specifically as follows:
(3) Under anhydrous conditions, 0.1g (0.7 mmol) of methyl orthosilicate, 1.4g (7.4 mmol) of titanium tetrachloride and 30mL (0.75 mol) of methanol are weighed and mixed uniformly in a reaction bottle, then 4g of alkoxy magnesium particles (containing about 35mmol of Mg) are poured into the reaction bottle, the mixture is transferred to a reaction kettle and transferred to an oven with the temperature of 80 ℃ for heterogeneous condensation reaction for 12 hours, and then the mixture is washed four times by absolute ethyl alcohol and hexane, separated and dried to obtain gel adhesion enhanced alkoxy magnesium composite particles.
Example 10
The same procedure as in example 1 was repeated except that the preparation stage of the composite particles of magnesium alkoxide was as follows:
(3) 5g (3.3 mmol) of methyl orthosilicate, 50g (26.4 mmol) of titanium tetrachloride and 100mL (2.5 mol) of methanol are weighed in a reaction bottle under anhydrous condition and uniformly mixed, then 2g of alkoxy magnesium particles (containing about 18mmol of Mg) are poured, the mixture is transferred into a reaction kettle and transferred into an oven with the temperature of 80 ℃ for heterogeneous condensation reaction for 12 hours, and then the mixture is washed four times with absolute ethyl alcohol and hexane, separated and dried to obtain the alkoxy magnesium composite particles with enhanced gel adhesion.
Comparative example 1
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. Fully replacing the reactor with high-purity nitrogen, adding 0.3g (1.1 mmol) of iodine, 120mL of mixed alcohol (ethanol and isooctanol, the molar ratio of ethanol to isooctanol is 2:0.05) and 30mL (0.28 mol) of toluene under the protection of nitrogen, stirring for 30min, and then cooling to 0 ℃; 6.3g (0.26 mol) of magnesium powder is added, the temperature is raised to 75 ℃ for reaction, the reaction is maintained at the reflux temperature for 4 hours, the mixture is washed four times by absolute ethyl alcohol and hexane, and the mixture is separated and dried to obtain white solid powder (magnesium alkoxide carrier) with good fluidity.
Into 300mL of a stirred 5-port reaction kettle with nitrogen fully replaced, 4g of the prepared magnesium diethoxide carrier and 40mL of toluene are added, the temperature is reduced to-15 ℃, and 20mL of TiCl is slowly added dropwise under stirring 4 When in use, the time is 1h; heating to 100deg.C, keeping the temperature for 2h, standing for settling, decanting supernatant, and adding 30mL TiCl again to the obtained solid 4 And 3mL of tetraethoxysilane, keeping the temperature for 1h, standing and settling, press-filtering the clear liquid, washing with 100mL of hexane for multiple times at 60 ℃ and drying to obtain the solid catalyst with good fluidity.
The particle size, distribution and polymerization product properties of the catalyst were measured by the same method as in example, and the results are shown in Table 1.
The performance parameters of the catalysts and polymers of the examples and comparative examples are shown in Table 1.
TABLE 1
| Numbering device | D50/μm | Span | Ac/KgPE/gCat | BD/g/cm 3 | Particle size<75μmwt％ |
| Example 1 | 44.64 | 0.78 | 34 | 0.39 | 0.03 |
| Example 2 | 45.32 | 1.01 | 32 | 0.37 | 0.06 |
| Example 3 | 44.05 | 0.98 | 33 | 0.36 | 0.17 |
| Example 4 | 43.89 | 1.01 | 34 | 0.30 | 0.22 |
| Example 5 | 44.38 | 1.02 | 32 | 0.32 | 0.25 |
| Example 6 | 44.67 | 1.01 | 33 | 0.30 | 0.73 |
| Example 7 | 36.72 | 0.99 | 35 | 0.34 | 0.21 |
| Example 8 | 58.89 | 1.02 | 32 | 0.30 | 0.18 |
| Example 9 | 43.96 | 0.80 | 34 | 0.33 | 0.56 |
| Example 10 | 46.02 | 0.91 | 31 | 0.31 | 0.05 |
| Comparative example 1 | 44.25 | 1.02 | 35 | 0.25 | 3.42 |
Description: in table 1, the data in the first and second columns represent the performance of the catalyst; column 3 shows the activity of the catalyst; the fifth column of column 4 shows the properties of the polymer.
As is clear from Table 1, the particle size distribution, average particle size and comparative example of the catalyst prepared in the examples of the present invention are equivalent. However, the introduction of the silicon precursor, the metal precursor, the alcohol or ether oxygen donor organic solvent in the catalyst is beneficial to improving the mechanical property of the alkoxy magnesium particles, so that the mechanical strength of the catalyst is improved, and the anti-crushing property is improved; thus, the catalyst of the present invention produced polymers having a significantly higher bulk density than the comparative examples and a much lower fines content than the comparative examples. Therefore, the catalyst has better comprehensive performance.
The embodiments of the present invention have been described above, the description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (12)
1. A process for preparing a polyolefin catalyst support, characterized in that the process comprises:
1) Adding a halogenating agent and mixed alcohol into an inert solvent under inert atmosphere, stirring for reaction, and cooling to-15-10 ℃;
2) Adding magnesium powder, heating to 60-90 ℃, reacting, filtering, washing and drying to obtain alkoxy magnesium particles;
3) Adding a silicon precursor and a metal precursor into an oxygen donor organic solvent, uniformly mixing, adding the alkoxy magnesium particles obtained in the step 2), reacting, filtering, washing and drying to obtain the polyolefin catalyst carrier.
2. The method of manufacturing according to claim 1, wherein:
in the step (1) of the process,
the inert atmosphere is selected from argon or nitrogen;
the inert solvent is at least one selected from benzene, toluene, xylene, hexane, heptane, octane, decane, white oil and paraffin; more preferably at least one from toluene, hexane, decane, heptane, white oil;
the halogenating agent is at least one of iodine simple substance, magnesium iodide, magnesium chloride and manganese chloride;
the mixed alcohol is at least one of a linear or branched monohydric alcohol or a polyhydric alcohol; preferably a mixed alcohol selected from the group consisting of C1-C10 alcohols, more preferably a mixed alcohol of ethanol and isooctanol, or a mixed alcohol of ethanol and butanol;
preferably, the molar content of isooctyl alcohol or butanol in the mixed alcohol is 1-20%.
3. The method of manufacturing as claimed in claim 2, wherein:
in the step 1), the reaction time is 10-120 min.
4. The method of manufacturing according to claim 1, wherein:
in the step 2) of the process, the process is carried out,
the average grain diameter of the magnesium powder is 50-300 mu m;
the reaction time is 1-12 h.
5. The method of manufacturing according to claim 1, wherein:
the mol ratio of the halogenating agent to the magnesium powder is (0.002-0.1): 1;
the mol ratio of the mixed alcohol to the magnesium powder is (2-15): 1.
6. The method of manufacturing according to claim 1, wherein:
in the step 3) of the method,
the silicon precursor is at least one selected from silicon chloride, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane and dipropyldipropoxysilane;
the metal precursor is inorganic metal halide or organic metal alkoxide, preferably at least one of titanium tetrachloride, butyl titanate, isopropyl titanate, zirconium oxychloride, zirconium isopropoxide, propyl zirconate, tin chloride, ferric tetrachloride and lanthanum chloride;
the oxygen donor organic solvent is an alcohol or ether solvent, preferably at least one selected from methanol, ethanol, propanol, isopropanol, butanol, pentanol, diethyl ether, isopropyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, tetrahydrofuran, and dioxane.
7. The method of manufacturing according to claim 6, wherein:
step 3), the reaction temperature is 50-160 ℃; the reaction time is 1-48 hours;
the molar ratio of the silicon precursor to magnesium is (0.01-2): 1, preferably (0.01-1): 1;
the molar ratio of the metal precursor to magnesium is (0.01-30): 1, preferably (0.1-20): 1;
the molar ratio of the oxygen donor organic solvent to magnesium is (10-300): 1, preferably (20-150): 1.
8. A polyolefin catalyst support obtainable by the process according to any of claims 1 to 7,
the polyolefin catalyst carrier is granular and similarSpherical, with average particle size of 10-60 μm, particle size distribution of 0.6-1.4, bulk density of 0.2-0.6 g/cm 3 。
9. A Ziegler-Natta catalyst component for the polymerization of olefins, characterized in that: a reaction product comprising the following components:
a) The catalyst support of claim 8;
b) A liquid titanium compound; the titanium compound has the general formula of Ti (OR) n X 4-n Wherein R is C 1 ～C 8 The alkyl, X is halogen atom, n is more than or equal to 0 and less than or equal to 4;
c) An internal electron donor compound.
10. The catalyst component of claim 9 in which:
the titanium compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl and Ti (OC) 2 H 5 ) 3 At least one of I; and/or the number of the groups of groups,
the internal electron donor compound is at least one of esters, ethers, phenols, ketones, carboxylic acids and organic siloxane compounds; preferably at least one of esters, ethers and organosiloxanes; more preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, succinic acid ester, diethyl ether, butyl ether, tetrahydrofuran, tetramethoxysilane, tetraethoxysilane.
11. A catalyst for olefin polymerization, characterized in that the catalyst comprises:
1) A catalyst component according to claim 9 or 10;
2) An organoaluminum compound;
the general formula of the organic aluminum compound is AlR m X 3-m Wherein R is hydrogen or C 1 ～C 20 And the alkyl group X is halogen atom, and m is more than 0 and less than or equal to 3.
12. Use of the catalyst of claim 11 in the polymerization of olefins.
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