CN105777953A - Main catalyst component for propylene polymerization and preparation method thereof - Google Patents
Main catalyst component for propylene polymerization and preparation method thereof Download PDFInfo
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- CN105777953A CN105777953A CN201410822204.3A CN201410822204A CN105777953A CN 105777953 A CN105777953 A CN 105777953A CN 201410822204 A CN201410822204 A CN 201410822204A CN 105777953 A CN105777953 A CN 105777953A
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- Prior art keywords
- compound
- phthalate
- catalyst
- propylene polymerization
- magnesium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- -1 phthalate compound Chemical class 0.000 claims abstract description 33
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 20
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 10
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001826 dimethylphthalate Drugs 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 43
- 238000009826 distribution Methods 0.000 abstract description 27
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 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 37
- 239000004743 Polypropylene Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000012216 screening Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 235000011147 magnesium chloride Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Chemical group 0.000 description 4
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- RYZZHQUICKTJHD-UHFFFAOYSA-N C(C)[Ti](OC)(OC)CC Chemical compound C(C)[Ti](OC)(OC)CC RYZZHQUICKTJHD-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- 101100493713 Caenorhabditis elegans bath-45 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N hex-2-ene Chemical class CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a catalyst component for propylene polymerization, a preparation method and application thereof, the catalyst component is prepared by reacting a magnesium compound, a liquid oxygen-containing titanium compound, a chlorine-containing compound, a phthalate compound and titanium tetrachloride, the prepared catalyst has good particle shape, uniform particle size distribution and less fine-divided content of a polymerization product, and is beneficial to the use of the catalyst on polymerization process devices such as propylene gas phase, bulk and the like.
Description
Technical field
The present invention relates to a kind of catalytic component for propylene polymerization or combined polymerization and catalyst thereof, and the preparation method of this catalytic component and purposes.
Background technology
Ziegler-Natta catalyst system is occupied an leading position in polyacrylic industrialized production, the stereoselectivity and copolymerization performance etc. that focus on the polymerization activity of catalyst, the particle shape of catalyst and particle size distribution, catalyst of its theoretical research.And in polyacrylic actual production, the problem paid close attention to the most is how to improve particle shape and the particle size distribution of the polypropylene powder produced.If produce polypropylene powder particle shape be spherical, particle size distribution is narrower, big block and fine powder content are less, the polymer powders glutinous wall in polymer reactor and caking phenomenon will be greatly reduced, also reduce powder blocking frequency in pipe conveying procedure simultaneously, can effectively extending the even running time of process units, the product quality of production also can be highly stable.
It is known that, in process units, the particle shape of polypropylene powder and particle size distribution are mainly controlled by the particle shape of catalyst and particle size distribution, so, the catalyst that preparation has good particle shape and particle size distribution is particularly important, and this is also one of R&D direction updating raising Ziegler-Natta catalyst in recent years.
In the prior art, in order to obtain the catalyst with good particle shape and narrow diameter distribution, people generally adopt following a few class methods to prepare catalyst.
First method is fusion method, it is to be dissolved in alcohol reagent by magnesium compounds such as magnesium chlorides to form fused mass at a certain temperature, then stirring and emulsifying fused mass in liquid medium, method solidification of molten thing by being quenched afterwards, form spherical carrier of catalyst, then complete the load formation catalyst of the electron donor compounds such as phthalic acid ester, titanium compound.The preparation method of such catalyst stirs method low temperature height, is published in patent US4469648, US4399054 and WO9844009.In addition, it is possible to by the method for spray cooling prepared by fused mass spherical carrier of catalyst, then other catalyst components of load finally give catalyst again, and such method is published in patent US5100849 and US4829034.Prepare the specific equipment of ball type carrier needs by the fused mass of magnesium compound to complete, bring certain difficulty to the preparation of catalyst.
Equations of The Second Kind method is reaction method, it directly adopts the magnesium compound with certain granules form and particle size distribution, such as diethoxy magnesium compound is initiation material, by reacting with the titanium compound containing chlorine or other chlorine-containing compounds, forming the magnesium chloride of nascent state, then the Donor compound such as load phthalic acid ester, titanium compound form catalyst again.This typical method is published in patent US5965478.In such method, the particle shape of diethoxy magnesium compound becomes the crucial governing factor of final catalyst granules form, although the method preparing catalyst is simple, but the diethoxy magnesium compound preparing good particle shape only has several companies few in number to grasp in the world, so using such method to prepare catalyst be subject to a definite limitation.
3rd class method is solwution method, it is to adopt the magnesium compound such as magnesium chloride or diethoxy magnesium, suitable solvent is selected to be dissolved by magnesium compound, it is subsequently adding other compound or changes the condition dissolved, obtain the solids containing magnesium, titanium and electron donor by the method precipitated, and obtain catalyst granules after being processed with excessive liquid titanium compound by this solids.Such method is in being published in Chinese patent CN85100997, CN1099041A, CN1229092.The shortcoming of such method is the particle diameter of catalyst granules and particle size distribution is entirely and is controlled by precipitation process, and this is the recrystallization process of magnesium carrier composition, and the control of its stability is relatively difficult.
Hence it is highly desirable to provide a kind of method for preparing catalyst suitable in propylene polymerization, this preparation method is simple, raw material is easy to get, and the requirement of equipment is low, the feature that the catalyst of preparation not only polymerization activity is high, and catalyst also to have particle shape good, the advantage such as narrow particle size distribution.
Summary of the invention
The present invention relates to a kind of main catalyst component for propylene homo conjunction or propylene and other а alpha-olefinic copolymerizations and preparation method thereof, including: a kind of magnesium compound, a kind of oxygen-containing titanium compound of liquid, a kind of chlorine-containing compound, a kind of phthalate compound and titanium tetrachloride etc..
The preparation method that the present invention provides a kind of main catalyst component for propylene polymerization, comprises the steps:
A. by the magnesium compound shown in logical formula I and the oxygen-containing titanium compound stirring and dissolving shown in logical formula II until clear solution.
B. the clear solution obtained by step a forms precipitation with the chlorine-containing compound haptoreaction shown in logical formula III；
C. the precipitation obtained by step b and phthalate compound react, and reaction temperature is 0～150 DEG C, and the response time is 0.5 minute to 5 hours, washing, obtain solids；
D. obtaining adding titanium tetrachloride in solids to step c to react, reaction temperature is 70～150 DEG C, and the response time is 0.5 minute to 5 hours, and washing is dry, obtains major catalyst powder；
Wherein, in every mole of magnesium compound, described oxygen-containing titanium compound content is 0.01～10 mole, described chlorine-containing compound content is 0.01～20 mole, described phthalate compound content is 0.1～1 mole, and described titanium tetrachloride content is 1-100 mole
Mg(OR1)nCl2-n(Ⅰ)
Ti(OR2)mCl4-m(Ⅱ)
MCli(Ⅲ)
In formula:
R1、R2Represent C respectively2～C20Alkyl；M represents metal or nonmetalloid；0≤n≤2；0≤m≤4；0<i≤4.
Described magnesium compound is preferably magnesium chloride and/or diethoxy magnesium.
Described oxygen-containing titanium compound is preferably metatitanic acid lipoid substance and mixture thereof.
Described metatitanic acid lipoid substance is preferably containing titanic liquefied compound.
Described it is preferably butyl titanate containing titanic liquefied compound.
Described chlorine-containing compound selects at least one in free Silicon chloride., Zirconium tetrachloride., boron chloride, Phosphorous chloride. and the formed group of aluminum chloride.
Described phthalate compound selects at least one in free dimethyl phthalate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, the formed group of diamyl phthalate.
Described magnesium compound is preferably magnesium chloride and/or diethoxy magnesium.
Described oxygen-containing titanium compound is preferably metatitanic acid lipoid substance and mixture thereof.
Described metatitanic acid lipoid substance is preferably containing titanic liquefied compound.
Described it is preferably butyl titanate containing titanic liquefied compound.
Described chlorine-containing compound selects at least one in free Silicon chloride., Zirconium tetrachloride., boron chloride, Phosphorous chloride. and the formed group of aluminum chloride.
Described phthalate compound selects at least one in free dimethyl phthalate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, the formed group of diamyl phthalate.
The present invention also can details are as follows:
The major catalyst of the present invention except there is higher polymerization activity, the advantages such as it is good that major catalyst also has particle shape, narrow particle size distribution.Such major catalyst is highly suitable for gas-phase polymerization process and the bulk technique of propylene, is particularly suited for gas-phase polymerization process.
Described magnesium compound is logical formula I Mg (OR such as1)nCl2-nShown in, in formula, R is C2～C20Alkyl, it is possible to be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤2, concrete compound such as MgCl2、Mg(OEt)Cl、Mg(OEt)2And the alkoxyl magnesium compound of long-chain, the organo-magnesium compound used in reaction is preferably diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, two octyloxy magnesium etc..
The oxygen-containing titanium compound of described liquid is logical formula II Ti (OR such as2)nCl4-nShown in, in formula, R is C2～C20Alkyl, it is possible to be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤4, it is preferred to use tetravalent titanium compound, because they are generally in a liquid state at normal temperatures, and also fine with the compatibility of some solvents under normal conditions.The compound of n=4 and their mixture in titanium compound preferred formula specifically used in reaction, such as purity titanium tetraethoxide, four titanium butoxide, titanium tetramethoxide, dimethoxy diethyl titanium, four hexyloxy titaniums, four the last of the ten Heavenly stems oxygen base titanium, benzyloxy-4 titanium, four phenoxide titaniums etc., wherein preferred four titanium butoxide
Described chlorine-containing compound is logical formula III MCl such asnShown in, in formula, M is metal or nonmetalloid, R5It is C2～C20Alkyl, it is possible to be saturated or undersaturated straight chain, side chain or closed chain, 0 < n≤4.The example of chlorine-containing compound includes: Silicon chloride., carbon tetrachloride, Zirconium tetrachloride., boron chloride, Phosphorous chloride. aluminum chloride etc., wherein preferred Silicon chloride..
The example of described phthalate compound has dimethyl phthalate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, diamyl phthalate etc., wherein preferred n-butyl phthalate, diisobutyl phthalate.
The main catalyst component of the present invention preferably employs the following step and is prepared:
(1) logical formula I compound and logical formula II compound react formation clear solution at a certain temperature.
(2) clear solution step (1) obtained forms precipitation with the compound haptoreaction of logical formula III compound；
(3) precipitation that step (2) obtains is contacted successively with phthalate and titanium tetrachloride, obtain catalyst suspension.
1, in the preparation process of major catalyst component of the present invention, ratio between each component is in that, in every general Formula (I) compound, logical formula II compound controls at 0.01～10 mole, preferably 0.05～5 mole, logical formula III compound controls at 0.01～20 mole, it is preferable that 0.2～12 mole, phthalate compound consumption controls at 0.1～1 mole, and titanium tetrachloride controls at 1-100 mole.
In the first step preparing catalyst, the temperature that magnesium compound and titanium compound contact with each other depends on the character of reactant, is typically chosen and carries out at a relatively high temperature dissolving advantageously, it is preferable that below the decomposition temperature of reactant, temperature is normally no higher than 200 DEG C, is generally not more than 150 DEG C.The time dissolved depends on character and the operating condition of reactant, and general selection of time is with till being obtained in that fully transparent solution, and required time is typically in 10 minutes to 20 hours, it is preferable that 4 to 10 hours.After magnesium compound and titanium compound dissolve, the magnesium titanium complex solution formed can mix use with inert diluent, inert diluent is generally selected from aliphatic or aromatic hydrocarbon based, such as benzene,toluene,xylene, iso-butane, pentane, hexane, heptane or hexamethylene and mixture thereof, general toluene or hexane are proper atent solvents.
The second step of catalyst preparing is alternatively referred to as settling step, completes the chlorination reaction of magnesium titanium complex in this step, and namely chlorine element replaces the alkoxyl in magnesium compound and titanium compound, so that liquid coordination compound Precipitation from solution.The contact method of magnesium titanium complex solution and chlorine-containing compound can adopt any of suitable method to carry out, can adopt and magnesium titanium complex solution is progressively added drop-wise to the mode in chlorine-containing compound solution, it would however also be possible to employ chlorine-containing compound solution is progressively added drop-wise to the mode in magnesium titanium complex solution.Rate of addition is generally selected not cause the hot-spot of reaction to be as the criterion, and is generally stirred being beneficial to proceeding smoothly of reaction in dropping process.In this precipitation step, temperature can control between 0～100 DEG C, it is preferable that between 20～80 DEG C.The response time of settling step should be long enough to obtain to be precipitated completely, and the response time can last 1 minute to 10 hours, it is preferable that 0.5～5 hour.
Experiment finds, after settling step, to carry out maturation process advantageous to the grain type ratio of major catalyst reaction a period of time at a certain temperature, it can make the size distribution narrow of major catalyst, the intensity of catalyst particle can also be improved, thus reducing major catalyst particle fragmentation phenomenon in catalysis propylene polymerization processes simultaneously.The temperature of maturation process is generally equivalent to or is higher than the temperature of precipitation, and the time of slaking reaction can control at 0.5～15 hour, it is preferable that 1～5 hour.
After carrying out maturation process, the phthalate compound adding requirement mixes with precipitate.Mixing temperature generally lower than the decomposition temperature of material, for convenience, to be typically chosen between 0～150 DEG C, it is preferable that between 50～130 DEG C.Incorporation time is typically chosen 0.5 minute to 5 hours, it is preferable that 30 minutes to 1 hour.
After adding phthalate compound process, generally to wash, to remove the by-product formed in excessive reactant and preparation process, any atent solvent is used equally to this washing step, such as can select iso-butane, pentane, hexane, heptane, hexamethylene and toluene etc., experiment is generally selected the atent solvent that toluene is washing.
After having washed, adding titanium tetrachloride and react, the titanium tetrachloride of demand can once add or add several times.If added several times, the method generally adopted is the stirring of reaction system to be stopped, standing sedimentation a period of time, after thing to be precipitated is deposited to lower floor, is removed by upper strata reactant liquor, then adds titanium tetrachloride consumption next time.Generally, the mode adding titanium tetrachloride several times is adopted to be more beneficial for the raising of catalyst activity.Add the reaction temperature after titanium tetrachloride and be typically chosen between 70～150 DEG C, it is preferable that between 90～130 DEG C.Incorporation time is typically chosen 0.5 to 5 hour, it is preferable that 2 to 4 hours.
The invention still further relates to a kind of catalyst for olefinic polymerization particularly propylene polymerization or combined polymerization, it comprises the product of following component:
The main catalyst component of (a) present invention；
B () a kind of formula is AlR'nX3-nOrgano-aluminum compound, in formula, R' is hydrogen or carbon number is the alkyl of 1～20, and X is halogen, and n is the number of 1 < n≤3.Particular compound is AlEt such as3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl etc..The mol ratio of the titanium in organo-aluminum compound and major catalyst controls 1～500；
C () a kind of formula is R "nSi(OR″')4-nThe alkyl that organosilan compounds, wherein R " for the alkyl of carbon atom 1-20, cycloalkyl or aryl, R " ' are carbon number 1-4, n is the integer of 1≤n≤3.Particular compound is phenyltrimethoxysila,e such as, phenyl triethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, n-pro-pyl trimethoxy silane.The mol ratio of organo-aluminum compound and silane compound controls at 0.1-200.
The catalyst that the present invention relates to is applicable to the combined polymerization of all polymerization or propylene and other alhpa olefins of olefinic polymerization particularly propylene, and wherein alhpa olefin adopts the one in ethylene alkene, butylene, amylene, hexene, octene, 4 methylpentenes 1.
Detailed description of the invention
With embodiment the present invention is described below, but and unrestricted invention scope.
The mean diameter of catalyst and the test of particle size distribution thereof
Catalyst sample is disperseed in hexane, adopts the size distribution curve of Malversizer laser particle size analyzer test sample, wherein
The mean diameter of catalyst provides with D (50)
Particle size distribution Span=(D (90)-D (10))/D (50) of catalyst
In formula D (50) be in the size distribution curve of Malversizer laser particle size analyzer test all granules 50% diameter lower than the diameter value of this value；D (10) is the diameter diameter value lower than this value of the 10% of whole granule；D (90) is the diameter diameter value lower than this value of the 90% of whole granule.
Polymerization catalyst performance evaluation
In 5L polymeric kettle, after gas-phase propene is sufficiently displaced from, at room temperature add 5mL triethyl aluminum (AlEt3) hexane solution (AlEt3Concentration is 0.5mmol/mL), the hexane solution (CHMMS concentration is 0.1mmol/mL) of 1mL Cyclohexyl Methyl Dimethoxysilane (CHMMS), 10mL anhydrous hexane and 20-25mg ingredient of solid catalyst.Close polymeric kettle, introduce the hydrogen of 0.1MPa and the liquid propene of 1.0kg；Under agitation in 10min, temperature is risen to 70 DEG C and starts to be polymerized timing, discharging after polymerization 1h.Polypropylene powder is weighed after drying, calculates the activity of catalyst, tests polypropylene powder melt index, and sieves.
Embodiment 1:
(1) weigh 10.2 grams of magnesium chlorides, add 78 milliliters of butyl titanates, 140 DEG C of stirring and dissolving until forming clear solution, solution temperature being down to room temperature, adds 200 milliliters of dry hexane diluted for use.
(2) solution that 20 milliliter of (1st) step obtains is taken, at normal temperatures, this solution is slowly added dropwise in the mixed liquor of 30 milliliters of hexanes and 20 milliliters of Silicon chloride., after being added dropwise to complete, bath 45 DEG C of stirring reactions of temperature 1 hour, bath 65 DEG C of stirring reactions of temperature 2 hours, obtain the suspension of solids.
(3) in the suspension of solids, add 0.5 milliliter of n-butyl phthalate, 90 DEG C of stirring reactions 1 hour, stop stirring, stand, sedimentation, removes the supernatant, adds toluene 80 milliliters, after stirring 5 minutes at 90 DEG C, stop stirring, stand, sedimentation, the removal supernatant, such repeated washing solids 3 times.
(4) in system, 80 milliliters of toluene are added, 10 milliliters of titanium tetrachlorides, at 110 DEG C of stirring reaction 2h, first wash solids three times with toluene by the method for step (3), then every time with 80 hexanes wash solids three times, temperature during washing controls at 60 DEG C.After having washed, when bath temperature 65 DEG C, purge with high pure nitrogen dry, obtain solids flowability powder.
The mean diameter (D (50)) of catalyst: 26 microns, particle diameter distribution width Span:0.6, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Embodiment 2
N-butyl phthalate in catalyst preparation step (3) is adjusted to diisobutyl phthalate adjustment, and other conditions are with embodiment 1.
The mean diameter (D (50)) of catalyst: 27 microns, particle diameter distribution width Span:0.6, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Embodiment 3
0.5 milliliter of n-butyl phthalate in catalyst preparation step (3) is adjusted to 0.3 milliliter, and other conditions are with embodiment 1.
The mean diameter (D (50)) of catalyst: 25 microns, particle diameter distribution width Span:0.6, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Embodiment 4
0.5 milliliter of n-butyl phthalate in catalyst preparation step (3) is adjusted to 0.3 milliliter of diisobutyl phthalate, and other conditions are with embodiment 1.
The mean diameter (D (50)) of catalyst: 25 microns, particle diameter distribution width Span:0.6, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Embodiment 5
10.2 grams of magnesium chlorides in catalyst preparation step (1) are adjusted to 12.7 grams of diethoxy magnesium, and other conditions are with embodiment 1.
The mean diameter (D (50)) of catalyst: 35 microns, particle diameter distribution width Span:0.9, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Comparative example 1
Method with reference to patent US5965478 embodiment 1 is prepared, and concrete grammar is as follows:
(1) (particle diameter D (50) is 35 microns to weigh 10 grams of diethoxy magnesium, particle diameter distribution width Span value is 1.1) add 70 milliliters of toluene, by stable for system temperature at 10 DEG C, it is slowly added dropwise the n-butyl phthalate of 30 milliliters of titanium tetrachlorides and 3.6 milliliters, after being added dropwise to complete, system temperature is risen to 90 DEG C, continuously stirred reaction 2 hours.Stop stirring, stand, sedimentation, remove the supernatant, add toluene 80 milliliters, after stirring 5 minutes at 90 DEG C, stop stirring, stand, sedimentation, remove the supernatant, such repeated washing solids 3 times.
(2) in system, again add 70 milliliters of toluene and 30 milliliters of titanium tetrachlorides, then system temperature is risen to 110 DEG C, continuously stirred reaction 2 hours, finally use hexanes wash solids instead 10 times by the method in step (1), each hexane consumption is 100 milliliters, and temperature during washing is 40 DEG C.After having washed, when bath temperature 65 DEG C, purge with high pure nitrogen dry, obtain solids flowability powder.
The mean diameter (D (50)) of catalyst: 30 microns, particle diameter distribution width Span:1.2, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Comparative example 2
(1) it is prepared for spherical MgC1 with reference to the method for patent US4469648 embodiment 12·2.85C2H5OH carrier.
(2) under agitation, by 5.0 grams of spherical MgC12·2.85C2H5OH carrier joins equipped with 150 milliliters of titanium tetrachlorides and is cooled in-25 DEG C of glass reaction bottles in advance, progressively it is warming up to 80 DEG C, adding the positive fourth vinegar of 1.1 milliliters of internal electron donor phthalic acids two to react 2 hours in 130 DEG C, wash 6 times with normal hexane, last vacuum drying obtains catalyst.
The mean diameter (D (50)) of catalyst: 55 microns, particle diameter distribution width Span:1.3, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Comparative example 3
Method with reference to patent CN85100997 embodiment 1 is prepared, and concrete grammar is as follows:
In the reactor that high pure nitrogen is replaced, it is sequentially added into anhydrous magnesium chloride 0.05 mole, toluene 75 milliliters, epoxychloropropane 0.1 mole and tributyl phosphate 0.03 mole, being warming up to 50 DEG C under stirring, and maintain 2 hours, solid constituent is completely dissolved, it is subsequently adding awkward 0.008 mole of phthalic acid, maintains stirring mixing 1 hour.Solution is cooled to-25 DEG C, in 1 hour, drips titanium tetrachloride 55 milliliters, be to slowly warm up to 80 DEG C, progressively precipitate out solids.Add n-butyl phthalate 0.0125 mole, 80 DEG C of stirring reactions 1 hour, wash twice with toluene 100 milliliters after filtration.After having washed, adding toluene 60 milliliters, titanium tetrachloride 40 milliliters, 90 DEG C of stirring reactions 2 hours, after hexane 100 milliliters washs four times, vacuum drying obtained catalyst.
The mean diameter (D (50)) of catalyst: 33 microns, particle diameter distribution width Span:1.3, the activity of catalyst and the screening result of polypropylene powder are as shown in table 1.
Can be seen that from the aggregated data of table 1, under same polymerizing condition, the catalyst grain size narrowly distributing of the present invention, its Span value is basic between 0.6-1.0, it is better than between the 1.0-2.0 of existing catalyst, due to particle shape print effect, the particle size distribution of resulting polymers is equally also narrower, crosses thick or meticulous particle all less in polymer.
Table 1
Claims (13)
1., for a preparation method for the main catalyst component of propylene polymerization, comprise the steps:
A. by the magnesium compound shown in logical formula I and the oxygen-containing titanium compound stirring and dissolving shown in logical formula II until clear solution.
B. the clear solution obtained by step a forms precipitation with the chlorine-containing compound haptoreaction shown in logical formula III；
C. the precipitation obtained by step b and phthalate compound react, and reaction temperature is 0～150 DEG C, and the response time is 0.5 minute to 5 hours, washing, obtain solids；
D. obtaining adding titanium tetrachloride in solids to step c to react, reaction temperature is 70～150 DEG C, and the response time is 0.5 minute to 5 hours, and washing is dry, obtains major catalyst powder；
Wherein, in every mole of magnesium compound, described oxygen-containing titanium compound content is 0.01～10 mole, described chlorine-containing compound content is 0.01～20 mole, described phthalate compound content is 0.1～1 mole, and described titanium tetrachloride content is 1-100 mole
Mg(OR1)nCl2-n(Ⅰ)
Ti(OR2)mCl4-m(Ⅱ)
MCli(Ⅲ)
In formula:
R1、R2Represent C respectively2～C20Alkyl；M represents metal or nonmetalloid；0≤n≤2；0≤m≤4；0<i≤4.
2. the method for preparing catalyst for propylene polymerization according to claim 1, its described magnesium compound is magnesium chloride and/or diethoxy magnesium.
3. the method for preparing catalyst for propylene polymerization according to claim 1, its described oxygen-containing titanium compound is metatitanic acid lipoid substance and mixture thereof.
4. the method for preparing catalyst for propylene polymerization according to claim 3, its described metatitanic acid lipoid substance is containing titanic liquefied compound.
5. the method for preparing catalyst for propylene polymerization according to claim 4, it is described is butyl titanate containing titanic liquefied compound.
6. the method for preparing catalyst for propylene polymerization according to claim 1, its described chlorine-containing compound selects at least one in free Silicon chloride., Zirconium tetrachloride., boron chloride, Phosphorous chloride. and the formed group of aluminum chloride.
7. the method for preparing catalyst for propylene polymerization according to claim 1, its described phthalate compound selects at least one in free dimethyl phthalate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, the formed group of diamyl phthalate.
8. the method for preparing catalyst for propylene polymerization according to claim 1, its described magnesium compound is magnesium chloride and/or diethoxy magnesium.
9. the method for preparing catalyst for propylene polymerization according to claim 1, its described oxygen-containing titanium compound is metatitanic acid lipoid substance and mixture thereof.
10. the method for preparing catalyst for propylene polymerization according to claim 1, its described metatitanic acid lipoid substance is containing titanic liquefied compound.
11. the preparation method of the main catalyst component for propylene polymerization according to claim 1, it is described is butyl titanate containing titanic liquefied compound.
12. the preparation method of the main catalyst component for propylene polymerization according to claim 1, its described chlorine-containing compound selects at least one in free Silicon chloride., Zirconium tetrachloride., boron chloride, Phosphorous chloride. and the formed group of aluminum chloride.
13. the preparation method of the main catalyst component for propylene polymerization according to claim 1, its described phthalate compound selects at least one in free dimethyl phthalate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, the formed group of diamyl phthalate.
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| CN112724284A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Solid catalyst component, preparation method thereof, olefin polymerization catalyst and application |
| CN112811438A (en) * | 2020-12-31 | 2021-05-18 | 中国石油天然气股份有限公司 | Phosphorus-containing faujasite and preparation method thereof |
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| CN102344505A (en) * | 2011-06-23 | 2012-02-08 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst containing carboxylic ester compounds, preparation and application thereof |
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| CN109438596A (en) * | 2018-12-13 | 2019-03-08 | 中国科学院长春应用化学研究所 | Catalyst, preparation method, using polyalcohol stephanoporate microballoons as the catalyst system of carrier and application method |
| CN112724284A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Solid catalyst component, preparation method thereof, olefin polymerization catalyst and application |
| CN112811438A (en) * | 2020-12-31 | 2021-05-18 | 中国石油天然气股份有限公司 | Phosphorus-containing faujasite and preparation method thereof |
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