CN108912257A - A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified - Google Patents
A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified Download PDFInfo
- Publication number
- CN108912257A CN108912257A CN201810771326.2A CN201810771326A CN108912257A CN 108912257 A CN108912257 A CN 108912257A CN 201810771326 A CN201810771326 A CN 201810771326A CN 108912257 A CN108912257 A CN 108912257A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- chromium
- compound
- catalyst
- carrier type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 86
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000004411 aluminium Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 230000004913 activation Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 28
- 239000011651 chromium Substances 0.000 claims description 26
- 229910052804 chromium Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001844 chromium Chemical class 0.000 claims description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 235000013847 iso-butane Nutrition 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 61
- 239000000741 silica gel Substances 0.000 description 29
- 229910002027 silica gel Inorganic materials 0.000 description 29
- 229960001866 silicon dioxide Drugs 0.000 description 29
- 230000000694 effects Effects 0.000 description 19
- -1 polyethylene Polymers 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000006353 environmental stress Effects 0.000 description 12
- 230000008961 swelling Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000071 blow moulding Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003426 co-catalyst Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 210000001161 mammalian embryo Anatomy 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N 3-methyl-2-pentanone Chemical compound CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- PNWJTIFZRHJYLK-UHFFFAOYSA-N CC(C)(C)O[Cr](=O)(=O)OC(C)(C)C Chemical compound CC(C)(C)O[Cr](=O)(=O)OC(C)(C)C PNWJTIFZRHJYLK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of preparation method and applications of the modified carrier type chromium-series catalyst of aluminium, this method includes that silica supports and aluminium compound and chromium compound are mixed into slurry, the weight percent of aluminium compound and silica supports is 1.5~6.0 weight %: 1, the weight percent of chromium compound and silica supports is 3.5~8.5 weight %: 1, and the specific surface area of silica supports is 250~330m22.3~2.8mL/g of/g, Kong Rongwei, content >=1000ppm of sodium oxide molybdena；Slurry removes moisture content by heat drying, and 80~280 DEG C of heat drying temperature, heat drying time is 1 point~24 hours；Generate the compound containing aluminium, chromium compound；Compound of the calcining containing aluminium, chromium compound, which becomes its activation, can be used for the carrier type chromium-series catalyst that the aluminium of polymerization reaction is modified, and calcination temperature is 400~1000 DEG C, and calcination time is 1~10 hour.Polymerization reaction in 1- alkene of the catalyst for ethylene and containing 3 to 8 carbon atoms.
Description
Technical field
The present invention relates to a kind of preparation method and applications of the modified carrier type chromium-series catalyst of aluminium, relate in particular to
A kind of modified carrier type chromium-series catalyst of the aluminium of the polymerization reaction of the alpha-olefin for ethylene and containing 3 to 8 carbon atoms
Preparation method.
Background technique
What extrusion grade polyvinyl resin was almost all produced using chromium-based catalysts, this is because chromium-based catalysts, no
Be same as Ziegler-Natta catalyst or metallocene catalyst, it can produce the resin of wide molecular weight distribution, be suitable for food and
Detergent, industrial container, general chemical bucket, tank, particularly fuel tank；There are also tubing, geomembrane, even film.This
Outside, there are also a lot of other important commercial applications；Especially for blow molding applications, the characteristic that chromium-based catalysts are given is only one
Without two, and there is very big benefit in commercialized application.
These characteristics, including the expansion during blow molding, also referred to as die swelling or measurement expansion.It refers to grasps in blow molding
When making, before mold closure, after polymer is extruded into melting pipe (referred to as type embryo), polymer is deployed into any journey outward
The measurement index of degree.If the polymer die swelling of melting is too small, after mold closes, under air pressure, the type embryo phase of expansion
Between, cavity body of mould cannot be completely filled with, and finally obtained bottle or part are defective.If the polymer of melting is swollen from mould
Swollen too big, mold is hemizygous to push down the wide type embryo in part when closing, and polymer parison is caused to lose, thus, it is invalid or useless to form
Product.In general, each Mould operation has own uniquely from the requirement of expansion rate, avoid too big or too small swollen from mould
It is swollen.
In Polymer Processing production process, it is necessary to which accurate control polymer die swell, die swell depend on
In polymer molecular structure, be more directly to be determined by its catalysts nature.This is why this kind of
Catalyst be commonly designed lower specific surface area, such as in 300~400m2/ g, in this way, in the surface-active point of silica gel
Between the probability that mutually fuses of polymerization reactant it is just high, the probability height mutually fused means to have more long-chain branch to enter poly-
Owner's chain is closed, polymer die swelling is advantageously reduced.
Most of chromium/silica-gel catalyst can generate very high die swelling, and a method for offsetting this tendency is exactly to mention
The activation temperature of high catalyst.Unfortunately, this also brings many shortcomings, such as：Lower molecular weight, narrow molecular weight point
Cloth has more branches in the low molecular weight end of the chain.These will be discussed in subsequent paragraph.
With catalyst prepared by the present invention, be it is distinguished, under relatively low activation temperature, can produce low from mould
The polymer of expansion, and many important physical properties of container can be improved.
For catalyst under high activation temperature, the physical property of polymer has loss, and one is exactly environmental stress resistance
It cracks (ESCR), also referred to as resistance to chemical attack, this is especially important for big hollow product such as bucket and other large-scale containers.
And in general, in low activation temperature, this performance is enhanced, because can provide higher molecular weight polyisoprene under low activation temperature
Object is closed, wider molecular weight distribution and has more highly branched chain in high molecular weight moieties, it can promote the composition of tie molecule chain, gathering
Object crystalline sheets are closed tightly to maintain together.Therefore, catalyst of the invention is that only one can be by using low activation temperature
Degree, polymer does not generate excessively high die swelling, and can have the catalyst of higher resisting environmental stress and cracking (ESCR).
Equally, if increasing calcining temperature, other performances of polymer container such as toughness, impact strength or anti-drop
It will damage.Under low calcination temperature, best toughness can be obtained, is that higher molecular weight can be provided because of it, wider point
Son amount is distributed and in the strand of high molecular weight, there is more branches.Therefore, catalyst of the invention be only one because
Low activation temperature can be used, is expanded without sacrificing, and the catalysis of the higher resisting environmental stress and cracking of polymer (ESCR) can be provided
Agent.
But low activation temperature can be such that the activity of catalyst reduces.An approach for improving catalyst activity is just to provide
The catalyst of high hole content regulation lattice.Kong Rong provided by the invention is 2.0~3.0ml/g, preferably 2.3~2.8ml/g, preferably
2.4~2.6ml/g.This can be provided high catalyst activity (complete broken), meanwhile, high polymer bulk density can be generated.This
The polyethylene bulk density that invention catalyst provides is usually in 450~530kg/m3.
Under low activation temperature, another approach for improving catalyst activity is exactly that a small amount of aluminium is added to catalyst,
It can increase surface acidity, by electron density of the weakening from chromium activated centre, it can be made more active with ethylene reaction,
It is exactly that activity is higher.It is inadequate that any aluminium salt is briefly, however added into catalyst formulation, because increasing catalyst
The aspect of specific surface acidity, the method for some insertion aluminium, is completely ineffective.In the present invention, aluminium is added in a manner of unique, only
Using only aluminium triformate.It also can achieve this effect with aluminium acetate and propionic acid aluminium, but during problem is activation, when they are calcined
When, a large amount of exothermic reaction is generated, the activation of catalyst can be damaged aluminum sinter on silica gel.And aluminium triformate can
This problem is avoided, slight exothermic reaction is only generated.
Inorganic aluminate cannot effectively be bundled in aluminium on silica-gel carrier surface, and it is unacceptable to generate other
Salt, these salt can activating equipment or murder by poisoning workers.This kind of unsuccessful load aluminium example includes：Aluminum sulfate or nitre
The application of sour aluminium and nitrous acid aluminium or aluminum halide, in calcining, aluminum sulfate can release sulfur dioxide, aluminum nitrate and nitrous acid
Aluminium can be released containing nitrogen oxide, aluminum halide, as chloride, bromide, iodide energy severe corrosion equipment.Therefore, it is improving
In terms of catalyst activity, adjoint heat release, toxic or etching problem are solved, catalyst of the invention is unique.
In addition to reducing activation temperature, aluminium triformate is added on chromium silica-gel catalyst, the wide molecular weight of polymer point can be also added
Cloth.Wider molecular weight distribution makes resin readily flowed during processing, and the environmental stress resistance that can also improve the blow molding trade mark is opened
Split the resistance to slow crack growth with tubing.
Another question is exactly chromium-based catalysts under low-down activation temperature, it is intended to produce high molecular weight
Polymer, it will force production operation by increase temperature of reactor, can be only achieved target molten index, be enough to cause sometimes
Dirtization.In other words, such catalyst usually has very low melt index responding ability.In general, we are highly desirable to
Chromium/silica-gel catalyst melt index responding ability is improved, the operation temperature of such reactor can reduce, in this way,
Activation temperature can further decrease, and polymer physics performance can additionally be improved, as toughness and resisting environmental stress and cracking.And pass through
Correctly plus aluminium method can be achieved on this point.Aluminium itself and torpescence, it influences chromium and widens molecular weight in low molecular weight side
Distribution, in this way, reducing average molecular weight (increasing melt index responding ability).In fact, being rung by observation melt index
The increase of stress is as a result, anyone can judge the validity of aluminium processing.
Aluminium is added into chromium/silica-gel catalyst by various technologies, for example in Journal of Catalysis,
Vol.76,p.29(1982),or US Patent 3887494,US Patent 3119569,US Patent 4053436,US
Patent 4041224,US Patent 4284527,or most recently US Patent 6489428or US
Patent 6200920, or Advances in Catalysis, 2010, chapter 3 narrations.Cogelled is perhaps one
Useful method, still, it the shortcomings that be exactly that produce such catalyst usually very expensive, so the cost used is also held high
It is expensive.A kind of method that aluminium is loaded to silica-gel carrier surface is but very cheap, however, effective load be aluminium must by with hydroxyl
Group reaction is directly loaded on Silica Surface, and be simply impregnated on silica gel with water-soluble al inorganic salt be it is invalid,
Because its aluminum metal compound for only leaving agglomerate or sheet on Silica Surface, can not effectively contact with chromium ion to shadow
Ring effect.
Therefore, in the present invention, aluminium triformate is specially suitable silicon source, because it is by reacting with Silica Surface hydroxyl,
Form the load layer that can be interacted well with chromium ion.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of high activity, the polymer of production is applied in blow molding field, tool
There are high resisting environmental stress and cracking, high tenacity and low die swelling feature.
It is a further object to provide a kind of improved methods that aluminium is added to and is gone in chrome catalysts.
The further object of the present invention be to provide it is a kind of can produce high fusion index, for producing bucket, fuel tank and large size
The catalyst of container polymer.
The further object of the present invention is to provide one kind suitable for slurry polymerization system, has high activity and Gao Dui
The catalyst of product density polymers.
The further object of the present invention is to provide a kind of follow-on method containing chrome catalysts.
Further aim of the present invention is just to provide a kind of chromium silica-gel catalyst of aluminium containing payload.
Further object of the present invention is to provide a kind of wide molecular weight distribution of production of having the ability, and has high resisting environmental stress and cracking
With the chromium-based catalysts of high impact polyethylene.
The technical scheme is that：
A kind of preparation method for the carrier type chromium-series catalyst that aluminium is modified, this method includes by silica supports and calorize
It closes object and chromium compound and is mixed into slurry, the weight percent of aluminium compound and silica supports is 1.5~6.0 weight %:
1, the weight percent of chromium compound and silica supports is 3.5~8.5 weight %: 1, the ratio of the silica supports
Surface area is 250~330m22.3~2.8mL/g of/g, Kong Rongwei, content >=1000ppm of sodium oxide molybdena；Slurry is dry by heating
Dry removing moisture content, 80~280 DEG C of heat drying temperature, heat drying time is 1 point~24 hours；It generates and contains aluminium, chromium compound
Compound；Compound of the calcining containing aluminium, chromium compound makes its activation, becomes and can be used for the carrier model that the aluminium of polymerization reaction is modified
Chromium-based catalysts, calcination temperature are 400~1000 DEG C, and calcination time is 1~10 hour,；In the modified chromium-based catalysts of the aluminium
Chromium content be 0.1~5.0wt%, aluminium content be 0.5~5.0wt%.
Chromium content preferably 0.5~1.5wt% in the modified chromium-based catalysts of heretofore described aluminium, aluminium content compared with
It is well 1.0~3.0wt%.
Heretofore described silica supports are with aluminium compound and chromium compound mixed method：Silica supports
With aluminium compound and chromium compound in aqueous solvent or alcohols solvent dip loading.
Heretofore described aluminium compound is aluminium triformate, and the chromium compound is chromium acetate.
The average grain diameter of heretofore described silica supports is 70 to 120 microns.
Heretofore described calcining makes its activation containing the compound of aluminium, chromium compound, and calcination temperature is 500~700 DEG C.
The application of the catalyst of the preparation method preparation of the modified carrier type chromium-series catalyst of aluminium of the present invention, it is special
Point is one of the modified carrier type chromium-series catalyst of the aluminium for ethylene with any alpha-olefin of the selection containing 3 to 8 carbon atoms
Kind or several polymerization reactions.
The application of the catalyst of the preparation method preparation of the modified carrier type chromium-series catalyst of aluminium of the present invention, it is special
Point is the modified carrier type chromium-series catalyst of the aluminium for ethylene and any alkene α-hydrocarbon one of the selection containing 3 to 8 carbon atoms
Kind or several polymerization reactions, the polymerization reaction are completed in the annular-pipe reactor using iso-butane as solvent, and reaction temperature exists
80~110 DEG C.
In the present invention, organic solvent and aqueous solvent are dissolved in for handling chromium/silica-gel catalyst aluminium compound.It
Be well-known compound, including aluminum carboxylate, have 1~4 carbon atom or aluminium acetylacetonate in each acid groups,
In, acetylacetone,2,4-pentanedione group may include substitute, these substitutes can be the alkyl group of 1~10 carbon atom, 6~12 carbon
The aryl group of atom.This kind of typical compound is aluminium triformate, aluminum acetate, propionic acid aluminium, butyric acid aluminium and aluminium acetylacetonate.Preferred aluminium
Compound is aluminium triformate.
Soluble aluminum compound means that they are easy to be dissolved in organic solvent, such as chloroform, alcohol, propyl alcohol or ketone
Class is such as：Methyl ethyl ketone.More preferably, they are water-soluble, are exactly preferably that at least 2 grams of aluminium can be dissolved in 4 grams of water or alcohol.With
The carrier that aluminium compound combines is a unbodied primary silica-gel carrier.This silica gel material can silica gel, silicon from catalytic level
It is selected in glue-aluminium oxide, silica gel-boron oxide, silica gel-titanium dioxide, silica gel-zirconium oxide and its mixture, the dioxy in silica gel
SiClx content is from 80~100%wt.It is preferred that dioxide-containing silica is more than 90%.
Preferred silica gel material has a relatively low specific surface area, and optional specific surface area range is from 150~400m2/ g,
Secondary is specific surface area from 200~350m2/ g, closer to being exactly specific surface area from 250~330m2/ g, preferably about 300m2/g。
If specific surface area is excessively high, it often reduces melt index response power.If specific surface area is too low, it often reduces activity.
Preferred silica gel material Kong Rong with higher, Kong Rong provided by the invention be 2.0~~3.0mL/g, preferably 2.3
~2.8mL/g, most preferably 2.4~2.6mL/g.This can be provided high catalyst activity (all broken), meanwhile, it can also produce
Raw high polymer powders bulk density.Lower hole, which holds, generates low melt index response power, however, taking out as only passed through solvent
The method mentioned obtains macropore and holds silica gel, it can greatly increase cost.
The bulk density of catalyst production polyethylene of the present invention is usually in 400~640kg/m3.Preferably 430~560kg/
m3, preferably 450~530kg/m3.Bulk density is measured according to the regulation of ASTM D1895-89：Polymer powders
It gently pats, is packed into and marks graduated cylindrical body, by weighing the weight of 100 milliliters of resins, calculate and obtain.
About 25 to 200 microns of this silica gel material average particle size particle size.Average particle size particle size of the invention, a kind of specification
It is from 40 to about 150 microns, another specification is from 70 to about 120 microns.It is most preferably exactly that average particle size particle size is big
About at 65 microns.The particle size of catalyst can often determine the particle size of polymer.In the present invention, very big to urge
Catalyst particles, due to toughness polymer wrap up, make it is other cannot be crushed, so will increase reactor operation difficulty because these
Large-sized polymers are not easy to convey along endless tube.And too many small particle i.e. fine powder and bad, because it is unfavorable
In diluted phase transport of the polymer powders after reactor comes out.
It is preferred that these silica gel should lack alkalinous metal residue, such as sodium as far as possible.The content of Na2O should be less than 2500ppm.It is preferred that
It is less than 1500ppm, preferably less than 1000ppm.The sodium of high-content often causes to be sintered, and melt index is caused to respond power in this way
It reduces.Before aluminium load, chromic salts and aluminium triformate are normally incorporated into water, are made into aqueous solution and silica gel is mixed together into slurry.
Then, these slurry remove moisture content by heat drying.Heating can be realized by many methods, for example by doing by spraying
Dry, expansion drying, fluidized bed heat drying alternatively, being replaced by heat emptying, or is placed in unlimited Flat bottom container progress electrostatic and does
It is dry, or rotary kiln is used, wait other known methods.This heating can be to be completed in dry air, is also possible to
In inert gas, for example nitrogen, or even can also be reducing gas, for example completed in hydrogen or carbon monoxide.Alternatively, heating
It can also complete under vacuum conditions.
The temperature of this drying steps can be from 80 DEG C of degree to 280 DEG C, preferably from 100 DEG C to 250 DEG C, preferably from 150
DEG C to 225 DEG C.Too low drying temperature will lead to drying not exclusively, and such aluminium ion can be reacted with water rather than and Silica Surface
Silanol reaction.And excessively high drying temperature can take off part silanol, thus reduce effective aluminium and silane
The quantity that alcohol groups combine.It for the load aluminium of specified rate, heats at high temperature, it will usually which the melt index for reducing catalyst is rung
Stress.The heating time range of carrier is from 1 minute to more than 24 hours.The preferred carrier drying time is small from 1 hour to 10
When.Preferably drying time is from 2 hours to 8 hour.
Silica gel is carried on sufficient amount of aluminium compound to carry, and is the weight in order to ensure finally calcining out aluminium in catalyst
Degree is measured, range is from about 0.5~5.0wt%, and preferred aluminium content is from 1.0~3.0wt%, preferably from about
1.5~3.0wt%.Soluble aluminium compound usually uses as a solution, in order to reaction polymer is as flat as possible
Be distributed on carrier surface, however, pure aluminium compound also can be used if operating conveniently, for example by using
Aluminium acetylacetonate is as aluminium compound.During calcining, the organic substance of aluminium compound volatilizees, thus in catalyst aluminium weight
Percentage is greater than the weight percent of aluminium in aluminium compound.
Aluminium compound can be loaded by way of vaporizing and coming into full contact with dry carrier.For example, levulinic
Ketone aluminium, which can be first evaporated, to be added in nitrogen, and then, these nitrogen are for fluidizing carrier.Alternatively, aluminium compound can be with the shape of solution
Formula is added dropwise in the fluidized bed for being maintained at drying temperature, which is enough to vaporize aluminium compound.No matter which kind of mode, calorize close
Object can be vaporized and be reacted with the silanol of Silica Surface.
Another carrying method of aluminium compound is exactly that aluminium compound is dissolved in organic solvent, and dry silica gel is impregnated into
Wherein, then, solvent is evaporated.Organic solvent can be hydro carbons, for example pentane, heptane, hexane, toluene perhaps kerosene or
Chlorinated solvent, for example methylene chloride or chloroform or alcohols, as isopropanol, methanol perhaps ketone for example acetone or methyl
Ethyl acetone.Preferred organic solvent is absolute alcohol.
Load to the chromium compound of carrier, the compound of usually water-soluble or organic solvent dissolution.It can be
It is intermediate or be added later before aluminium compound addition.And the aqueous solution of preferably chromium compound.Example includes ammonium chromate,
Chromic acetate, chromic nitrate, chromium trioxide；Two aromatic hydrocarbons chromium compounds, for example diisopropylbenzene (DIPB) chromium；Esters, for example di-t-butyl chromate；
And chelate, for example chromium acetylacetonate.Chromium can also be loaded by the method for co-precipitation
Property solution is added in pure silica hydrogel, and then, mixture is dried, such as by furnace dried, tray dried,
Spray drying etc..Or be impregnated into the water-soluble solution of chromium on dry silica-gel mixture, then, mixture is as above
As described, dry again.If the chromium compound of load is organic solvent soluble, it is usually water-soluble to be different from
Mode carrys out dry silica gel, after solvent removal, generates the silica gel that macropore holds, the melt index of final catalyst can be made to respond energy
Power is improved.On calcined catalyst, the range of chromium content is about 0.001~10wt%, preferably 0.1~5wt%, most
It is well 0.5~1.5wt%, on the basis of calcined vehicle weight.
The method which kind of addition chromium compound no matter selected, it is all to pass through calcining that final, which includes the compound of aluminium compound,
Mode come be allowed to activation become polymerizable reaction catalyst, calcining is carried out in the air that high temperature contains oxygen, calcining
Temperature is normally controlled between 400 DEG C to 1000 DEG C, preferably between 450 DEG C to 800 DEG C, preferably at 500 DEG C to 650
℃.Activation of catalyst can be completed by calcining in purely dry air, alternatively, it also can be in the environment of reduction, example
Such as by providing carbon monoxide and air, activation is continued to complete, as United States Patent (USP) U.S 4151122, disclosed data exists
This is for reference only.And in terminal stage, the catalyst activated also can be by Carbon monoxide reduction, and reduction temperature temperature about exists
Between 300~600 DEG C.
It is most suitable for being applied to according to catalyst produced by the invention carrying out polymerization reaction in the environment of slurry, for example, such as beauty
As the open disclosure of state's patent 3248179.Simply, polymerization usually carries out in dry Inert hydrocarbon diluents, this
Diluent can be iso-butane, normal heptane, hexahydrotoluene or benzene etc., and range of reaction temperature is 60 DEG C~110 DEG C, reaction
Pressure is handled after 1.7~4.1Mpa, polymer recovery with CO2 or H2O, and purpose is exactly the catalyst of inactivating residual.Together
When, also stablize polymer performance using antioxidant, such as butylated hydroxytoluene (BHT) or antioxidant 1010, then passes through normal
Rule method is dry to obtain final polymer.As well-known technique, point that hydrogen controls polymer in the reactor can be used
Son amount.Polymerization reaction can have a rest progress in stirred tank inner room, can also with settling leg or without annular-pipe reactor into
Row can also be carried out in continuous multiple reactors.Catalyst of the invention can also be used for solwution method, vapor phase method or other often
Polymerization technique is advised, but compared to the technique that can produce higher melting index polymer, preferred slurry polymerization processes.
Catalyst of the invention is suitble to produce general Alathon, can also produce the copolymerization based on vinyl monomer
Object.Ethylene can be copolymerized with one or more higher aliphatic list alpha-olefin, and these comonomers can be containing 3~
The aliphatic alpha-olefin of 10 carbon atoms, for example propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene, be also possible to containing 4~
The conjugated diene of 12 carbon atoms.Therefore, in copolyreaction, vinyl monomer content range usually from 93~99.6wt%,
Rest part is higher alkene comonomer, and in the ethylene copolymer obtained in this way, ethylene contents reach 97~99.6wt%.?
It is more widely applied in range, ethylene copolymer can use the ethylene and 20~0.2wt% comonomer of 80~99.8wt%
To prepare production.
Catalyst of the invention, which also can be used metal alkyl and mention as co-catalyst, carrys out high catalyst activity, it is entire
The general rule of polyethylene industry.The example of such co-catalyst includes triethyl aluminum, trimethyl aluminium, triisobutyl aluminium, triethyl group
Boron, tri butyl boron, silane, lithium methide, butyl lithium, magnesium ethide, dibutylmagnesium etc..These co-catalyst typical amounts are
0~10ppm (wt/wt), using the weight of solvent of reactor as calculating benchmark.Alternatively, can also be with co-catalyst in reactor
Chromium content molar ratio as calculating benchmark, the molar ratio range of these co-catalysts is from 0~10, preferably 0~5, preferably
It is 0~3, preferably 0~1.The co-catalyst of higher concentration can change polymer produced, and pass through in-situ copolymerization monomer
Generation causes density polymer to reduce.
Catalyst of the invention is commonly used to the production relatively high polymer of molecular weight.For example, the polymer usually produced
Melt index be lower than 0.2dg/10min, preferably less than 0.1dg/10min, more preferably less than 0.05dg/10min, it is optimal
Choosing is less than 0.025dg/10min.Or catalyst of the invention is commonly used to the polymer of production, it is molten under high load capacity
Melt index (HLMI) lower than 25dg/10min, preferably less than 15dg/10min, more preferably less than 8dg/10min, most preferably
It is less than 5dg/10min.Melt index (MI) measurement：According in standard ASTM D1238-E, condition 190/2, at 190 DEG C,
It is measured with 2160 grams of counterweights, unit is gram/10 minutes.High load melt index (MI) measurement：According to standard ASTMD1238-F
In, condition 190/21.6 is measured at 190 DEG C with 21600 grams of counterweights, and unit is gram/10 minutes.It is catalyzed with other chromium systems
Agent is compared, and under identical reaction conditions, the polymer of catalyst production of the invention usually has higher HLMI/MI ratio
Rate.This is important in major blowing preparation, because it influences die swelling.In general, reaction temperature is greater than 100 DEG C of productions
Polymer, HLMI/MI ratio be greater than 75, preferably greater than 90, be more preferably greater than 100, preferably greater than 120.Certainly,
HLMI/MI ratio additionally depends on reactor condition, especially temperature, if temperature is lower, which can be increased.HLMI/MI ratio
Rate also depends on the target MI of produced polymer, and perhaps HLMI lower MI or HLMI tends to produce higher HLMI/MI
Shearing ratio.
Catalyst of the invention is commonly used to production copolymer, by ethylene and alpha-olefin, for example 1- butylene, 1- hexene or
Person's 1- octene carries out copolyreaction completion.By reducing the crystallinity or density of polymer, so that the toughness of polymer is more preferable.
In general, catalyst of the invention be used to production density be 0.940~0.970g/mL polymer, preferably 0.945~
0.965g/mL is more preferably 0.948~0.956g/mL, most preferably 0.948~0.954g/mL.The density measurement of polymer：
According to the program C measurement in standard ASTMD1505-8 and ASTM D1928, polymer tabletting sample preparation, sample is with the speed of 15 DEG C/hr
Degree cooling, measures after storing about 40 hours at room temperature, is indicated with polymer weight (g/cc) per cubic centimeter.The present invention
Polymer of the catalyst commonly used to produce high resisting environmental stress and cracking (ESCR).Normally, catalyst of the invention is used to
The polymer that resisting environmental stress and cracking is higher than 1000 hours is produced, preferably greater than 1200 hours, it is small to be more preferably greater than 1500
When, most preferably greater than 2000 hours.Resisting environmental stress and cracking (ESCR, hour) is according to the condition in standard ASTM D1693
A measurement.
Detailed description of the invention
Fig. 1 is blow molding operation schematic diagram of the invention.
Specific embodiment
The present invention is described in further detail below by embodiment, but embodiment protects model to the present invention by no means
The limitation enclosed.
Embodiment 1
A kind of preparation method of the modified carrier type chromium-series catalyst of aluminium of the invention includes the following steps：
Selection specific surface is 250m2/ g, Kong Rongwei 2.3ml/g, Na2O content is 1000ppm, and average grain diameter D50 is
110 μm of silica supports；The configured chromium acetate aqueous solution for being 0.5wt% containing chromium is put by 60 grams of silica supports
50ml and containing aluminium be 1.5wt% formic acid aluminum water solution 50ml mixed solution in impregnates 4 hours generation slurry, filtering, 100
The raw catalyst containing aluminium, chromium complexes catalyst is made at DEG C after drying.Raw catalyst 550 DEG C temperature lower calcination 4 hours, system
Catalyst after must activating.
Embodiment 2
A kind of preparation method of the modified carrier type chromium-series catalyst of aluminium of the invention includes the following steps：
Selection specific surface is 300m2/ g, Kong Rongwei 2.51ml/g；Na2O content is 1000ppm, and average grain diameter D50 is
110 μm of silica supports；The configured chromium acetate aqueous solution for being 1.0wt% containing chromium is put by 60 grams of silica supports
50ml and containing aluminium be 2.0wt% formic acid aluminum water solution 50ml mixed solution in impregnates 4 hours generation slurry, filtering, 100
The raw catalyst containing aluminium, chromium complexes catalyst is made at DEG C after drying.Raw catalyst 550 DEG C temperature lower calcination 4 hours, system
Catalyst after must activating.
Embodiment 3
A kind of preparation method of the modified carrier type chromium-series catalyst of aluminium of the invention includes the following steps：
Selection specific surface is 330m2/ g, Kong Rongwei 2.8ml/g, Na2O content is 1000ppm, and average grain diameter D50 is
110 μm of silica supports；The configured chromium acetate aqueous solution for being 1.5wt% containing chromium is put by 60 grams of silica supports
50ml and containing aluminium be 3.0wt% formic acid aluminum water solution 50ml mixed solution in impregnates 4 hours generation slurry, filtering, 100
The raw catalyst containing aluminium, chromium complexes catalyst is made at DEG C after drying.Raw catalyst 550 DEG C temperature lower calcination 4 hours, system
Catalyst after must activating.
Polymerization evaluation
Polymerization evaluation uses the catalyst after activation.Polymerization reaction evaluates 4 liters of stainless steels that blender is equipped at one
It is carried out in reactor, mixing speed is in 1000rpm.There is stainless steel clamp set around reactor, have coolant liquid in collet, passes through heat exchange
Device reaction temperature undulated control within 1 DEG C, implemented by electronic control equipment by accurate temperature control.
Unless otherwise indicated, the polymerization evaluation in embodiment carries out in following manner：Firstly, (usual 0.01 gram a small amount of
To 0.10 gram) solid catalyst under nitrogen protection, be added in dry reactor, then, 1200 grams of isobutyl be added
Alkane liquid, reactor are heated to specified temperature, usually at 105 DEG C or so.Finally, ethylene is added to reactor, reach one
A suitable fixation pressure during test, maintains always this pressure usually in 3.65MPa.When continuously stirring specified
Between, usually in 1 hour, the pressure of setting is maintained, the flow of reactor is entered by recording ethylene, it is known that catalyst
Activity.
After the completion of reaction, ethylene feed is cut off, reactor slowly pressure release and is opened, and polymer powders are recycled.Any
In the case of, it is necessary to reactor is cleaned out, it cannot remaining any wall built-up object or other dirty compounds.Then, polymer powders are dry
After dry and weigh.The catalyst activity polymer of the production of catalyst per hour per gram weight (gram polyethylene/gram catalyst/
Hour) indicate.
Melt index (MI) measurement：According in standard ASTM D1238-E, condition 190/2, at 190 DEG C, with 2160 grams
Counterweight measurement, unit is gram/10 minutes.
High load melt index (HLMI) measurement：According in standard ASTM D1238-F, condition 190/21.6, at 190 DEG C
Under, it is measured with 21600 grams of counterweights, unit is gram/10 minutes.
The density measurement of polymer：According to the program C measurement in standard ASTM D1505-68 and ASTM D1928, polymerization
Object melts mould pressing sample, and sample is cooling with the speed of 15 DEG C/hr, measures after storing about 40 hours at room temperature, with every cube li
The polymer weight (g/cc) of rice indicates.
Resisting environmental stress and cracking (ESCR, hour) is according to the condition A measurement in standard ASTM D1693.
The following examples and comparative example demonstrate three component parts of catalyst, silica gel, aluminium and chromium it is important
Property, which dictates that the activity of final catalyst and the final products performance of polymer produced and blow molding performance.Simultaneously
Demonstrate the importance that silica gel hole holds selection and catalyst activation temperature.The nine different types of catalyst of our test evaluations, all
It is attempt to for producing major blowing containers resin.These test evaluation results arrange in table 1 below.HLMI target is 10~
12, density targets are 0.955.Embodiment 2 represents optimal catalyst and polymer.In other any one comparative examples
In, change a catalyst variable in embodiment 2.Die swelling, resisting environmental stress and cracking and anti-dropping drop impact (fall distance
The container for needing to cause to be full of is damaged) as shown in table 1.
Table 1：The correlation of polymer performance and different catalysts and response variable
In table 1, sample 2 is the modified carrier type chromium-series catalyst of aluminium prepared by the preparation method of embodiment 2.Remaining
Sample be comparative example 1, chromium-based catalysts used in 3-7 respectively.
Embodiment 2 and comparative example 1 compare, and show the importance for adding aluminium.Notice the catalyst of addition aluminium in work
Property, be all significantly increased in terms of ESCR, anti-dropping drop impact.Melt index responding ability also increases, it is as shown in the table HLMI higher, and only
Need lower reaction temperature that can reach this HLMI.Shear loading also increases, and shows that the polymer of production is easy to squeeze out.
Embodiment 2 and comparative example 3 compare, and show that the aluminium of addition is more than that 2.0% will not cause any performance improvement.
Almost all of polymer performance does not change.
Embodiment 2 and comparative example 4 compare, and show that silica gel specific surface area increases to 520m2The influence of/g.Activity is slightly
Increase, ESCR and anti-dropping drop impact are also the same.It is noted, however, that melt index responding ability declines, it is meant that need by mentioning
High reaction temperature, fall in melt index within specification.More importantly die swelling is increased to except specification, this is
It is unacceptable.In addition, shear loading declines, so that polymer extrusion is more difficult.
Embodiment 2 and comparative example 5 compare, and illustrate the influence of the Kong Rong of catalyst.In example 5, hole holds drop, urges
The decline of agent activity, the decline of melt index responding ability, it is meant that need reaction temperature to improve very more.Die swelling is substantially
It reduces, this is not necessarily good thing, and ESCR and anti-dropping drop impact are also decreased obviously.
Embodiment 2 and comparative example 6 compare, and illustrate the influence for reducing density.ESCR and anti-dropping drop impact are sharply increased.
This is predictable, because crystallinity has dropped, caused by the toughness increase of polymer.Die swelling is not by too big shadow
It rings.
Embodiment 2 and comparative example 7 compare, and illustrate the influence for increasing activation temperature.As expected, catalyst activity
It is significantly increased with melt index responding ability, it is as shown in the table, even if reducing reaction temperature, HLMI is still increased.Due to compared with
High HLMI, shear loading also slightly reduce.Die swelling also dramatically declines, and shows that higher calcination temperature is undesirable.
Also observe that ESCR is greatly decreased together with anti-dropping drop impact.
On the right side of table, two commercially available catalyst are also listed, also test evaluation is compared.PQ24340 and reality
It applies example 2 to be made of closely similar, but all relatively low by the ESCR and anti-dropping drop impact of its resulting polymers, melt index is rung
Should be able to power also these slightly lower phenomenons, deducibility：Although the aluminium content of PQ24340 is high, aluminium effectively participates in the low efficiency of reaction.
Finally enter that table 1 compares is 7510 catalyst of Grace Sylopol, it does not have aluminium, meanwhile, hole holds relatively low.
The melt index responding ability of this catalyst is excessively poor, and it is as shown in the table, and reaction temperature is set to maximum value, and HLMI can only also reach
To 7.2.Although HLMI is low, ESCR is very poor, and having compared with highly resistance dropping shock is the polymer molecular weight having benefited from
Increase.
Claims (8)
1. a kind of preparation method of the modified carrier type chromium-series catalyst of aluminium, which is characterized in that this method includes by silica
Carrier and aluminium compound and chromium compound are mixed into slurry, and the weight percent of aluminium compound and silica supports is 1.5~
The weight percent of 6.0 weight %: 1, chromium compound and silica supports is 3.5~8.5 weight %: 1, the titanium dioxide
The specific surface area of silicon carrier is 250~330m22.3~2.8mL/g of/g, Kong Rongwei, content >=1000ppm of sodium oxide molybdena；Slurry
Moisture content is removed by heat drying, 80~280 DEG C of heat drying temperature, heat drying time is 1 point~24 hours；Generation contains
The compound of aluminium, chromium compound；Compound of the calcining containing aluminium, chromium compound changes its activation as the aluminium that can be used for polymerization reaction
Property carrier type chromium-series catalyst, calcination temperature be 400~1000 DEG C, calcination time be 1~10 hour,；The modified chromium of the aluminium
Chromium content in series catalysts is 0.1~5.0wt%, and aluminium content is 0.5~5.0wt%.
2. the preparation method of the modified carrier type chromium-series catalyst of aluminium according to claim 1, which is characterized in that described
Chromium content in modified chromium-based catalysts is 0.5~1.5wt%, and aluminium content is 1.5~3.0wt%.
3. the preparation method of the modified carrier type chromium-series catalyst of aluminium according to claim 1, which is characterized in that described
Silica supports are with aluminium compound and chromium compound mixed method：Silica supports exist with aluminium compound and chromium compound
Dip loading in aqueous solvent or alcohols solvent.
4. the preparation method of the modified carrier type chromium-series catalyst of aluminium according to claim 1, which is characterized in that described
Aluminium compound is aluminium triformate, and the chromium compound is chromium acetate.
5. the preparation method of the modified carrier type chromium-series catalyst of aluminium according to claim 1, which is characterized in that described
The average grain diameter of silica supports is 70 to 120 microns.
6. the preparation method of the modified carrier type chromium-series catalyst of aluminium according to claim 1, which is characterized in that described
Compound of the calcining containing aluminium, chromium compound makes its activation, and calcination temperature is 500~700 DEG C.
7. a kind of preparation method of the carrier type chromium-series catalyst modified according to aluminium described in claim 1-5 any claim
The application of the catalyst of preparation, which is characterized in that the modified carrier type chromium-series catalyst of the aluminium contains for ethylene and any selection
There is the polymerization reaction of one or more of 1- alkene of 3 to 8 carbon atoms.
8. a kind of preparation method of the carrier type chromium-series catalyst modified according to aluminium described in claim 1-5 any claim
The application of the catalyst of preparation, which is characterized in that the modified carrier type chromium-series catalyst of the aluminium contains for ethylene and any selection
There is the polymerization reaction of one or more of 1- alkene of 3 to 8 carbon atoms, which is using iso-butane as solvent
It is completed in annular-pipe reactor, reaction temperature is at 80~110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810771326.2A CN108912257A (en) | 2018-07-13 | 2018-07-13 | A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810771326.2A CN108912257A (en) | 2018-07-13 | 2018-07-13 | A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108912257A true CN108912257A (en) | 2018-11-30 |
Family
ID=64410123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810771326.2A Pending CN108912257A (en) | 2018-07-13 | 2018-07-13 | A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108912257A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277523A (en) * | 2021-06-01 | 2021-08-20 | 钦州东辰材料科技有限公司 | Preparation method of silica gel carrier for olefin polymerization catalyst |
| CN115175946A (en) * | 2020-02-28 | 2022-10-11 | 埃科维斯特催化剂技术有限责任公司 | Silica supported chromium catalyst and method for producing same |
| US11732065B2 (en) * | 2020-02-28 | 2023-08-22 | Pq Corporation | Chromium-on-silica catalysts and methods of making the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895770A (en) * | 1995-02-28 | 1999-04-20 | Pq Corporation | Olefin polymerization catalysts with specific silica supports |
| CN101896508A (en) * | 2007-10-26 | 2010-11-24 | Pq硅石英国有限公司 | Catalyst precursor particles, their preparation and use |
| CN102286123A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | catalyst component of ethylene polymerization and preparation method thereof |
-
2018
- 2018-07-13 CN CN201810771326.2A patent/CN108912257A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895770A (en) * | 1995-02-28 | 1999-04-20 | Pq Corporation | Olefin polymerization catalysts with specific silica supports |
| CN101896508A (en) * | 2007-10-26 | 2010-11-24 | Pq硅石英国有限公司 | Catalyst precursor particles, their preparation and use |
| CN102286123A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | catalyst component of ethylene polymerization and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115175946A (en) * | 2020-02-28 | 2022-10-11 | 埃科维斯特催化剂技术有限责任公司 | Silica supported chromium catalyst and method for producing same |
| US11732065B2 (en) * | 2020-02-28 | 2023-08-22 | Pq Corporation | Chromium-on-silica catalysts and methods of making the same |
| US20230365725A1 (en) * | 2020-02-28 | 2023-11-16 | Yatao Rachel Hu | Chromium-on-silica catalysts and methods of making the same |
| CN113277523A (en) * | 2021-06-01 | 2021-08-20 | 钦州东辰材料科技有限公司 | Preparation method of silica gel carrier for olefin polymerization catalyst |
| CN113277523B (en) * | 2021-06-01 | 2023-05-26 | 钦州东辰材料科技有限公司 | Preparation method of silica gel carrier for olefin polymerization catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1891125B1 (en) | Catalyst compositions comprising small silica support materials and methods of use in polymerization reactions | |
| JP5337484B2 (en) | Blow molded polyethylene resin | |
| EP2183286B1 (en) | Continuity additives and their use in polymerization processes | |
| CN108641027B (en) | Method for controlling polyolefin properties during polymerization | |
| BRPI0317788B1 (en) | process for the production of an ethylene polymer | |
| EP1789459B1 (en) | Polyolefins | |
| CN108912257A (en) | A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified | |
| HU182055B (en) | Process for preparing an impregnated polymerisation catalyst composition and for the copolymerisation of ethylene by means of the catalyst composition | |
| KR20080112295A (en) | Chromium-based catalysts | |
| CN102257017B (en) | Method for seed bed treatment for polymerization reaction | |
| AU2005240979A1 (en) | Chromium based polymerization catalyst, the method to prepare it and polymers prepared therewith | |
| EP3341427B1 (en) | Ethylene gas phase polymerisation process | |
| JP2016204649A (en) | Polymer particle of soft polymer and manufacturing method therefor | |
| CN100497400C (en) | Process for preparing titanium modified supported chromium catalyst and its use | |
| CN102356098B (en) | Methods of preparing a polymerization catalyst | |
| US7754834B2 (en) | Bulk density promoting agents in a gas-phase polymerization process to achieve a bulk particle density | |
| JP2016204648A (en) | Drying method of polymer powder | |
| KR20130139860A (en) | Ziegler-natta type catalysts, methods of preparing same, polymers produced using the catalysts and articles produced therefrom | |
| CN107001516B (en) | Chromium-based catalyst composition for olefin polymerization | |
| WO2020064484A1 (en) | A multi-stage process for producing a c2 to c8 olefin polymer composition | |
| Pullukat et al. | Porous silica in transition metal polymerization catalysts | |
| US20090156762A1 (en) | Methods of Preparing a Polymerization Catalyst | |
| JPS58157806A (en) | Polymerization catalyst | |
| CN112166128A (en) | Activator-nucleator formulations | |
| Sun et al. | The Influences of Structural Feature and Surface Properties of Montmorillonite on the Supported Olefin Polymerization Catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181130 |
|
| RJ01 | Rejection of invention patent application after publication |