CN102453154A - Organic chromium catalyst for ethylene polymerization and preparation method thereof - Google Patents
Organic chromium catalyst for ethylene polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN102453154A CN102453154A CN2010105150350A CN201010515035A CN102453154A CN 102453154 A CN102453154 A CN 102453154A CN 2010105150350 A CN2010105150350 A CN 2010105150350A CN 201010515035 A CN201010515035 A CN 201010515035A CN 102453154 A CN102453154 A CN 102453154A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- chromium
- catalyst
- pentane
- ethylene polymerization
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000011651 chromium Substances 0.000 title claims abstract description 73
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 61
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 49
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000005977 Ethylene Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 29
- -1 alkyl silane chromate Chemical class 0.000 claims abstract description 26
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- QWHNJUXXYKPLQM-UHFFFAOYSA-N dimethyl cyclopentane Natural products CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000001844 chromium Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910000423 chromium oxide Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HDRDGWRBSHNNQS-UHFFFAOYSA-L [Cr](=O)(=O)(O)O.C1(=CC=CC=C1)[SiH](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cr](=O)(=O)(O)O.C1(=CC=CC=C1)[SiH](C1=CC=CC=C1)C1=CC=CC=C1 HDRDGWRBSHNNQS-UHFFFAOYSA-L 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CQBWEBXPMRPCSI-UHFFFAOYSA-M O[Cr](O[SiH3])(=O)=O Chemical compound O[Cr](O[SiH3])(=O)=O CQBWEBXPMRPCSI-UHFFFAOYSA-M 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- OQDZZSNMQPRDGZ-UHFFFAOYSA-N Triphenethylsilane Chemical compound C=1C=CC=CC=1CC[SiH](CCC=1C=CC=CC=1)CCC1=CC=CC=C1 OQDZZSNMQPRDGZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- DKRDVQXZJNVXDP-UHFFFAOYSA-M bromo(dibutyl)alumane Chemical compound [Br-].CCCC[Al+]CCCC DKRDVQXZJNVXDP-UHFFFAOYSA-M 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YRICGUHIUWWNGJ-UHFFFAOYSA-N decyl(hydroxy)silane Chemical class C(CCCCCCCCC)[SiH2]O YRICGUHIUWWNGJ-UHFFFAOYSA-N 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- MSJGTVVKAYQMPX-UHFFFAOYSA-N diethyl(propoxy)alumane Chemical compound CCC[O-].CC[Al+]CC MSJGTVVKAYQMPX-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002977 hyperthermial effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- REQXNMOSXYEQLM-UHFFFAOYSA-N methoxy-dimethyl-phenylsilane Chemical compound CO[Si](C)(C)C1=CC=CC=C1 REQXNMOSXYEQLM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 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
- 239000012071 phase Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 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
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension 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
- NKLIVVJLUBFSTE-UHFFFAOYSA-N tribenzyl(hydroxy)silane Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)(O)CC1=CC=CC=C1 NKLIVVJLUBFSTE-UHFFFAOYSA-N 0.000 description 1
- JYVWRCIOZLRMKO-UHFFFAOYSA-N tributyl(hydroxy)silane Chemical compound CCCC[Si](O)(CCCC)CCCC JYVWRCIOZLRMKO-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention is aAn organic chromium catalyst for ethylene polymerization and a preparation method thereof. The catalyst comprises a main active catalyst, an inorganic oxide carrier, a modifier and a cocatalyst, wherein A. the main active catalyst is chromium salt, and the content of the chromium salt in the total mass of the catalyst is 0.01-5%; B. the technical requirement that the carrier is an inorganic oxide is as follows: a. the surface area is about 200-700m2(ii)/g; b. pore volume of about 1 to 4 cc/g; c. the pore diameter is about 60-700
Description
Technical field
The present invention is a kind of ethylene polymerization organic chromium Catalysts and its preparation method.Belong to ethylene rolymerization catalyst.Be particularly related to loading type organic chromium catalyst for ethylene polymerization and preparation method thereof.
Background technology
Chromium-based catalysts is applied in the poly production as an important kind of ethylene rolymerization catalyst the earliest.From initial at silica gel (Si0
2) or silica gel-aluminum oxide (SiO
2-Al
2O
3) upward the research of supported chromium is successful so far, people have found the preparation method of silica gel and the relative molecular mass (being designated hereinafter simply as molecular weight) that the activation method behind the load chromium-based catalysts can change product.The supported chrome series catalysts has been widely used in solution method, slurry process, the vapor phase process PE production technique.The PE resin that chromium-based catalysts makes can process in slush molding fields such as bottle, jar that shape is complicated, the processing rotatory better, cut bad mouth and melting the thicker product of part, this is because this resin contains long-chain branch component and a small amount of ultra-high molecular weight (about 10
7) component, thereby make its processing characteristics more superior.
In the PE production process, traditional chromium oxide catalyst is owing to exist that induction time is long, the product melting index is low, copolymerization performance is poor, hydrogen is transferred shortcomings such as insensitive, thereby more and more can not satisfy in the application people to the products made thereby performance demands.For this reason, at 20th century the mid-1970s, UCC, chemical companies such as Phillips actively improve chromium-based catalysts.
USP2,825,721 disclosed loading type chromium oxide catalysts are chromium trioxide or at least can partial oxygen under the high temperature oxidation condition change into the compound of chromium trioxide, in the aqueous solution, load to prepare on the silica gel.This catalyzer has overcome the complicated shortcoming of active ingredient synthesis technique, has reduced the catalyzer cost, but narrower with the product molecular weight distribution of this Preparation of Catalyst.
USP3,324,095 disclosed loading type silane chromate ester catalysts, carrier is an inorganic oxide, and active ingredient is the silane chromate ester, and promotor is a kind ofly to have at least 1 or be no more than 2 organo-aluminium compounds that are connected in the alkoxyl group on the aluminium atom; Molecular weight is higher, the extrusion molding level product of MWD broad though this catalyzer can be used for preparing, and the synthesis technique of this catalyst activity component is complicated, and catalyzer is cost an arm and a leg.
Have high reactivity, certain induction time by the polyethylene catalysts of chromic oxide preparation, can produce polymkeric substance with HMW and intermediate molecular weight distribution.Catalyst activity based on silyl chromate is lower, but can produce the polymkeric substance than wide molecular weight distribution.Silyl chromate Catalyst Production cost is higher than the chromium oxide catalyst price usually.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of active height, induction time to suit, be applicable to the ethylene polymerization organic chromium catalyzer of the polyethylene product of producing the broad range of molecular weight distributions.
The present invention also aims to provide the ethylene polymerization organic chromium Preparation of catalysts method that a kind of synthesis technique is simple, manufacturing cost is lower.
The object of the invention can reach through following measure:
Ethylene polymerization organic chromium catalyzer of the present invention comprises main body active catalyst, inorganic oxide carrier, properties-correcting agent and promotor, wherein:
A. said main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.01-5%
The said carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is about 200-700m
2/ g;
B. pore volume is about 1-4cc/g;
C. the aperture is about 60-700
D. particle size is about 10-200 μ m;
C. said properties-correcting agent is that preparation alkyl silane chromate ester catalyst reclaims liquid;
D. said promotor is the alkylate of aluminium, lithium, boron, zinc.
Said chromic salts is selected from oxide compound, acetate, carboxylate salt, dichromate, the chromic salt of chromium.Can be one or more organic or inorganic chromic salts, wherein the oxidation valence state of chromium be 0-6.Chromic salts in the present invention also comprises chromium metal.Generally, the chemical formula of chromic salts is CrXn, and X can be with can be different in the formula; Can be any organic or inorganic group, n be an integer, and its value is the typical organic radical of 1-6.; Each group can contain about 1-20 carbon atom, can be alkyl alkoxy, ester group, ketone group and/or carboxamido-group.Organic radical can be: straight chain base or contain the base of side chain, and cyclic group or acyclic radical, aryl or aliphatic group, and can constitute by blended aliphatic group, aryl and/or cyclic aliphatic base.Typical inorganic chromium compound has: the nitrate salt of the acetate of chromium, dichromate, chromic salt, chromium and the oxide compound of chromium etc.The oxide compound of the acetate of preferred chromium, the nitrate salt of chromium and chromium, the more preferably acetate of chromium.
The catalyst recovery liquid that said properties-correcting agent produces on the inorganic, metal oxide carrier for the alkyl silane chromate loads to.The properties-correcting agent staple is alkylsilanol and unreactive hydrocarbons solvent.The alkylsilanol structural formula is R
3SiOH.Wherein, R represents the alkyl in the alkylsilanol, alkyl can be identical also can be different, and should have 1-14 carbon atom.Alkylsilanol can include but not limited to trimethyl silicane alkanol, triethyl silicane alcohol, tributyl silanol, triisopentyl silanol, three-2-ethylhexyl silanol, three decyl silanols, three (14) base silane alcohol, tribenzyl silanol, triphen ethylsilane alcohol, triphenyl silanol, trimethylphenyl silanol etc. among the present invention, especially preferred triphenyl silanol.The alkylsilanol strength of solution is 1 * 10
-6-100mol/L, preferred 1 * 10
-5-10mol/L, more preferably 1 * 10
-4-1mol/L.
Said promotor is the alkyl organometallic compound, and alkyl metal cpd can be the alkylate of aluminium, lithium, boron, zinc, preferred alkyl aluminum compound among the present invention.
Adoptable organo-aluminium compound is alkylaluminium cpd and alkoxy aluminum compound, and alkylaluminium cpd has: trialkyl aluminium compound, aluminum alkyl halide and alkyl aluminum hydride.Usually, the alkyl of aluminum alkyls can be identical also can be different, and should have 1-14 carbon atom, halogen then is fluorine, chlorine, bromine and iodine.Concrete alkylaluminium cpd includes but not limited to, trimethylaluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, dibutyl aluminum bromide and close compound.Usually, alkoxy aluminum compound has general formula R
2-Al-0R; Wherein alkyl can be identical also can be different; And should have 1-14 carbon atom; The example includes but not limited to, oxyethyl group diethyl aluminum, methoxyl group diethyl aluminum, oxyethyl group dimethyl-aluminium, oxyethyl group di-isopropyl aluminium, propoxy-diethyl aluminum, oxyethyl group diisobutyl aluminum and ethoxyl methyl aluminium triethyl.Select triethyl aluminum among the embodiment for use, not should be appreciated that the present invention is so limited.
The object of the invention can also reach through following measure:
Ethylene polymerization organic chromium catalyzer of the present invention is characterized in that
A. said main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.1-1.5%
The said carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is about 245-500m
2/ g;
B. pore volume is about 1.5-3cc/g;
C. the aperture is about 100-300
D. particle size is about 40-150 μ m;
C. said properties-correcting agent is that the alkyl silane chromate loads to the recovery liquid that produces in the support of the catalyst process;
But the alkylate of D. said promotor aluminium, lithium, boron, zinc.
Ethylene polymerization organic chromium catalyzer of the present invention, inorganic oxide carrier described in the B is any one that from silica gel, aluminum oxide, phosphagel phosphaljel, titanium oxide, chooses, perhaps its any two or more combinations.
Ethylene polymerization organic chromium catalyzer of the present invention, the effective constituent of properties-correcting agent described in the C is alkylsilanol.
Ethylene polymerization organic chromium catalyzer of the present invention, described in the D in the promotor metallic element and main body active catalyst chromium element mol ratio be 0.1-50.
Ethylene polymerization organic chromium catalyzer of the present invention, promotor described in the D can join in the catalyzer before the polymerization catalyst reaction, also can add in the polymerization system on the spot in polymerization process.
A kind of ethylene polymerization organic chromium Preparation of catalysts method of the present invention is provided below the present invention, comprises the steps:
A. dipping, prebake
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 0.5-48 hour;
C. roasting
Through the dried catalyzer of step B, under 300-950 ℃ of temperature, in the oxidizing atmosphere, roasting 0.5-48 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection; Add modifier solution, under 45 ℃ of temperature, lucifuge reaction 0.5-20 hour; Said modifier solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Saturated naphthenic hydrocarbon is like hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; Aromatic hydrocarbons is like in the benzene,toluene,xylene any one.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, said alkyl metal cpd solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Saturated naphthenic hydrocarbon is like hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; Aromatic hydrocarbons is like in the benzene,toluene,xylene any one.
Be a kind of ethylene polymerization organic chromium catalyzer preferred manufacturing procedure of the present invention below, it is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-24 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 1-24 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection; Add modifier solution, under 45 ℃ of temperature, lucifuge reaction 1-15 hour; Said modifier solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, said alkyl metal cpd solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
Be another kind of ethylene polymerization organic chromium catalyzer preferred manufacturing procedure of the present invention below, it is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-12 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 4-12 hour;
In this step, the compound of chromium is oxidized to the oxide compound of high valence state; During hyperthermic treatment; Remain unchanged after can once rising to a certain temperature, also can temperature-gradient method, promptly after rising to a certain temperature maintenance certain hour; Continue to be warming up to another temperature maintenance certain hour, process is kept in this intensification one can be divided into several times as required.
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, adds modifier solution, under 45 ℃ of temperature, and lucifuge reaction 2-10 hour, said modifier solution, the organic solvent of employing is an iso-pentane.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, said alkyl metal cpd solution, the organic solvent of employing is an iso-pentane.
Catalyzer of the present invention both can be used for the alkene homopolymerization, also can be used for the copolymerization of alkene.Said homopolymerization is meant is not having to make alkene such as ethene carry out polymerization under the situation of comonomer.Said copolymerization is meant by olefinic monomer such as ethene and contains the linearity of 3-20 carbon atom or the monomeric polyreaction of high alpha-olefin of branching.Wherein, the high alpha-olefin monomer that is fit to includes, but not limited to propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene and 3,5,5-trimethylammonium-1-hexene etc.
The present invention is applicable to known devices and reaction conditions, through any suspension, solution, slurry or gas phase process olefin polymerization and it is not limited to the polymerization system of any particular type.Slurry polymerization system generally includes the reactor drum that adds olefinic monomer and catalyst composition, and said reactor drum contains to be useful on and dissolves or the polyolefinic liquid reaction medium that suspends.Liquid reaction medium can be made up of for non-reacted inert liquid hydrocarbon down a large amount of liquid monomers or employed polymerizing condition.Although said inert liquid hydrocarbon needn't act on catalyst composition or the effect of the polymer solvent that obtained by this method, its is usually with acting on the monomeric solvent that in polyreaction, uses.The unreactive hydrocarbons that are suitable for this purpose are Trimethylmethane, iso-pentane, hexane, hexanaphthene, heptane, benzene, toluene etc.Olefinic monomer contacts with reactivity between the catalyst composition and should or stir and keep through continuously stirring.To contain the monomeric reaction medium of olefin polymer product and unreacted alkene extracts from reactor drum continuously.Separate olefin polymer product, and unreacted alkene monomer and liquid reaction medium are recycled in the reactor drum.
The present invention is equally applicable to gas phase polymerization system.Usually, conventional gas fluidized-bed process is under reaction conditions, under the catalyzer existence condition, the air-flow of one or more olefinic monomers is passed through fluidized-bed reactor continuously being enough to the solids bed is remained under the speed of suspended state.The air-flow that will contain unreacted monomer takes out continuously from reactor drum, compresses, cooling, optional part or total condensation and be recycled to reactor drum.Product taken out from reactor drum and add monomer join in the recirculated air.Temperature control for polymerization system is needed, also can exist for catalyzer and any gas of reactant inert at gas flow.
The disclosed technical scheme of ethylene polymerization organic chromium Catalysts and its preparation method of the present invention, comparing prior art has following positively effect:
1. provide a kind of active height, induction time to suit, be applicable to the ethylene polymerization organic chromium catalyzer of the polyethylene product of producing the broad range of molecular weight distributions.
2. the ethylene polymerization organic chromium Preparation of catalysts method that a kind of synthesis technique is simple, manufacturing cost is lower is provided.
3. the relative chromium oxide catalyst of catalyzer of the present invention has clear improvement in performances such as polyvinyl resin product molecular weight distribution, copolymerization performance, hydrogen accent susceptibilitys.
4. adopt two (tri-phenyl-silane) chromate/SiO 2 catalysts of the inventive method preparation with low cost, economic benefit is obvious.The cost of catalyst preparation described in the present invention is practiced thrift more than 50% than traditional double (tri-phenyl-silane) chromate/SiO 2 catalyst, and cost is lower.
Embodiment
The present invention below will make further detailed description through embodiment:
Embodiment 1
Taking by weighing concentration is the chromium acetate aqueous solution 0.87g of 50wt%, and its chromium content is 11.5wt%, adds deionized water 56ml.The chromium acetate aqueous solution for preparing is joined in 20g Davison 955 silica gel, mixed the back dipping 6 hours, 60-120 ℃ of oven dry more than 12 hours in air atmosphere then.The bottom that then that drying is good catalyst Precursors is put into Φ 30 * 500mm is welded with the silica tube activator of sintered quartz grid distributor, and the high pure nitrogen that feeds through dehydration and deoxidation makes catalyst fluidization.Intensification heated quarty tube activator was kept 2 hours at 200 ℃, made catalyzer further remove moisture; Be warming up to 325 ℃, switch to the dry air of dehydration, be warming up to 600 ℃; Kept 4 hours; Again switchback high pure nitrogen at last, device to be activated is cooled to room temperature, takes out chromium oxide catalyst and places nitrogen atmosphere to store for future use.Get the 1g chromium oxide catalyst and place the catalyst preparation bottle, adding TPS concentration is 3.84 * 10
-3The PS properties-correcting agent 12.5ml of mol/L, 45 ℃ of lucifuges were reacted 2.5 hours.Press Al/Cr=20 and add triethyl aluminum, stirred 1 hour, blow down solvent with high purity nitrogen then, process chromium content 0.5wt%, Al/Cr=20, the PS0.5 catalyzer of TPS: Cr=0.5 (mol ratio).
Embodiment 2-5
Embodiment 2-5 and embodiment 1 similar process, difference are that PS properties-correcting agent dosage is different.Among the embodiment 2, PS properties-correcting agent dosage 25ml, TPS: Cr=1.0; Among the embodiment 3, PS properties-correcting agent dosage 18.75ml, TPS: Cr=1.5; Among the embodiment 4, PS properties-correcting agent dosage 25ml, TPS: Cr=2.0; Among the embodiment 5, PS properties-correcting agent 20.83ml, TPS: Cr=3.0.
Comparative Examples 1
Get Davidson 955 silica gel 20g, the bottom of putting into Φ 30 * 500mm is welded with the silica tube activator of sintered quartz grid distributor, and the high pure nitrogen that feeds through dehydration and deoxidation makes catalyst fluidization.Intensification heated quarty tube activator was kept 2 hours at 200 ℃, made catalyzer further remove moisture, continued to be warming up to 600 ℃, kept 4 hours, and device to be activated then is cooled to room temperature, took out 955 good silica gel of activation and placed nitrogen atmosphere to store for future use.Take out 955 good silica gel 1g of activation, place the catalyst preparation bottle, add the 30ml iso-pentane, be warming up to 45 ℃, add two (tri-phenyl-silane) chromate 0.06g, lucifuge reaction 2.5 hours.Press Al/Cr=20 and add triethyl aluminum, stirred 1 hour, blow down solvent with high purity nitrogen then, process chromium content 0.5wt%, two (tri-phenyl-silane) chromate (BC) catalyzer of Al/Cr=20.
Embodiment 1-5, Comparative Examples 1 are carried out the polymerization evaluation, and experimental result is seen table 1,2:
Table 1 polymerizing condition: 85 ℃, pressure: normal pressure, polymerization time: 1 hour
Explain:
Modifier concentration 3.84 * 10 among the embodiment 1,2
-3Mol/L;
Modifier concentration 7.68 * 10 among the embodiment 3,4
-3Mol/L;
Modifier concentration 1.15 * 10 among the embodiment 5
-2Mol/L.
Table 2 polymerizing condition: 85 ℃, pressure: normal pressure, polymerization time: 1 hour
Embodiment 6
Taking by weighing concentration is the chromium acetate aqueous solution 0.87g of 50wt%, and its chromium content is 11.5wt%, adds deionized water 56ml.The chromium acetate aqueous solution for preparing is joined in 20g Davison 955 silica gel, mixed the back dipping 6 hours, 60-120 ℃ of oven dry more than 12 hours in air atmosphere then.The bottom that then that drying is good catalyst Precursors is put into Φ 30 * 500mm is welded with the silica tube activator of sintered quartz grid distributor, and the high pure nitrogen that feeds through dehydration and deoxidation makes catalyst fluidization.Intensification heated quarty tube activator was kept 2 hours at 200 ℃, made catalyzer further remove moisture; Be warming up to 325 ℃, switch to the dry air of dehydration, be warming up to 600 ℃; Kept 4 hours; Again switchback high pure nitrogen at last, device to be activated is cooled to room temperature, takes out chromium oxide catalyst and places nitrogen atmosphere to store for future use.Get the 1g chromium oxide catalyst and place the catalyst preparation bottle, adding TPS concentration is 7.68 * 10
-3The PS properties-correcting agent 18.75ml of mol/L, 45 ℃ of lucifuges were reacted 2.5 hours.Press Al/Cr=20 and add triethyl aluminum, stirred 1 hour, blow down solvent with high purity nitrogen then, process chromium content 0.5wt%, Al/Cr=15, the PS1.5 catalyzer of TPS: Cr=1.5 (mol ratio).
Embodiment 7-11
Embodiment 7-11 and embodiment 6 are basic identical, just in polymerization process, have added comonomer 1-hexene, and 1-hexene adding proportion is respectively 1,3,5,8,10 by volume among the embodiment 7-11.Embodiment 6-11 is carried out the polymerization evaluation response, and experimental result is seen table 3:
Table 3 polymerizing condition: 85 ℃, pressure: normal pressure, polymerization time: 1 hour
Explain:
The description of analytical methods that adopts among the embodiment is following:
The dsc analysis method is following among the embodiment: adopt Pyris Diamond DSC polymer samples to be carried out mensuration such as fusing point.TR :-100～300 ℃; Temperature accuracy: 0.01 ℃; Dynamic range: 0.2uw～800mw; Calorimetric precision: 0.1%.
Molecular-weight determination is measured as follows among the embodiment: molecular weight of polyethylene adopts viscosimetry to measure, and makes solvent with perhydronaphthalene, 135 ℃ of temperature, and Ubbelohde viscometer records intrinsic viscosity.Calculate molecular weight according to formula.
Mn＝5.37×10
4×[η]
1.37
The catalyst experiment chamber is estimated and is adopted the polymerization of normal pressure slurry polymerization reactor, and the built-in magnetic agitation of reaction kettle uses the oil bath system that polymerization reactor is heated.Polyreaction is carried out as follows: reactor heating, charge into high pure nitrogen, and get rid of then, vacuumize again, so the repeated treatments polymerization reactor is 10 times.Charge into ethene, in reaction kettle, add catalyzer then, the beginning polyreaction.Calculate polymer yield by following formula:
W
PE＝(Q·60)/(t
poly·w
cat)
Wherein Q is polymerization time t
Poly(minute) productive rate (g) of interpolymer, w
CatBe catalyst levels.Polyreaction adds a certain amount of ethanol after finishing in polymer, termination reaction emits reaction gas, reclaims polyethylene product.
Claims (9)
1. an ethylene polymerization organic chromium catalyzer is characterized in that comprising main body active catalyst, inorganic oxide carrier, properties-correcting agent and promotor, wherein:
A. said main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.01-5%
The said carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is about 200-700m
2/ g;
B. pore volume is about 1-4cc/g;
C. the aperture is about 60-700
D. particle size is about 10-200 μ m;
C. said properties-correcting agent is that preparation alkyl silane chromate ester catalyst reclaims liquid;
D. said promotor is the alkylate of aluminium, lithium, boron, zinc.
2. according to the ethylene polymerization organic chromium catalyzer of claim 1, it is characterized in that
A. said main body active catalyst is a chromic salts, and its content in the catalyzer total mass is 0.1-1.5%
The said carrier of B is that the technical requirements of inorganic oxide is:
A. surface-area is about 245-500m
2/ g;
B. pore volume is about 1.5-3cc/g;
C. the aperture is about 100-300
D. particle size is about 40-150 μ m;
C. said properties-correcting agent is that the alkyl silane chromate loads to the recovery liquid that produces in the support of the catalyst process;
But the alkylate of D. said promotor aluminium, lithium, boron, zinc.
3. according to the ethylene polymerization organic chromium catalyzer of claim 1, it is characterized in that inorganic oxide carrier described in the B is any one that from silica gel, aluminum oxide, phosphagel phosphaljel, titanium oxide, chooses, perhaps its any two or more combinations.
4. according to the ethylene polymerization organic chromium catalyzer of claim 1, the effective constituent that it is characterized in that properties-correcting agent described in the C is alkylsilanol.
5. according to the ethylene polymerization organic chromium catalyzer of claim 1, it is characterized in that described in the D that metallic element and main body active catalyst chromium element mol ratio are 0.1-50 in the promotor.
6. according to the ethylene polymerization organic chromium catalyzer of claim 1, it is characterized in that promotor described in the D can join in the catalyzer, also can add in the polymerization system in polymerization process on the spot before the polymerization catalyst reaction.
7. the ethylene polymerization organic chromium Preparation of catalysts method of a claim 1 is characterized in that comprising the steps:
A. dipping, prebake
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 0.5-48 hour;
C. roasting
Through the dried catalyzer of step B, under 300-950 ℃ of temperature, in the oxidizing atmosphere, roasting 0.5-48 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection; Add modifier solution, under 45 ℃ of temperature, lucifuge reaction 0.5-20 hour; Said modifier solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Saturated naphthenic hydrocarbon is like hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; Aromatic hydrocarbons is like in the benzene,toluene,xylene any one.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, said alkyl metal cpd solution, the organic solvent of employing are iso-pentane, pentane, hexane, heptane, pure kerosene and other similar alkane; Saturated naphthenic hydrocarbon is like hexanaphthene, pentamethylene, dimethylcyclopentane, methylcyclohexane and other loop-like alkane; Aromatic hydrocarbons is like in the benzene,toluene,xylene any one.
8. the ethylene polymerization organic chromium Preparation of catalysts method of a claim 1 is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-24 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 1-24 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection; Add modifier solution, under 45 ℃ of temperature, lucifuge reaction 1-15 hour; Said modifier solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, said alkyl metal cpd solution, the organic solvent of employing are any one in iso-pentane, pentane, normal hexane, the heptane.
9. the ethylene polymerization organic chromium Preparation of catalysts method of a claim 1 is characterized in that comprising the steps:
A. flood
According to the content of the chromium in the main body active catalyst in the catalyzer total mass is the ratio of 0.01-5%, will contain chromium cpd solution, is impregnated on the inorganic oxide carrier, 60-120 ℃ of prebake 12 hours;
B. dry
Catalyzer after steps A prebake, under 0-300 ℃ of temperature, in the inert atmosphere, dry 1-12 hour;
C. roasting
Through the dried catalyzer of step B, under 300-850 ℃ of temperature, in the oxidizing atmosphere, roasting 4-12 hour;
D. modification
The catalyzer that step C is baked places the equipment of inert atmosphere protection, adds modifier solution, under 45 ℃ of temperature, and lucifuge reaction 2-10 hour, said modifier solution, the organic solvent of employing is an iso-pentane.
E. reduction
In the catalyzer after step D modification, add promotor alkyl metal cpd solution, reducing catalyst, said alkyl metal cpd solution, the organic solvent of employing is an iso-pentane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105150350A CN102453154B (en) | 2010-10-22 | 2010-10-22 | Organic chromium catalyst for ethylene polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105150350A CN102453154B (en) | 2010-10-22 | 2010-10-22 | Organic chromium catalyst for ethylene polymerization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102453154A true CN102453154A (en) | 2012-05-16 |
| CN102453154B CN102453154B (en) | 2013-07-24 |
Family
ID=46036873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105150350A Active CN102453154B (en) | 2010-10-22 | 2010-10-22 | Organic chromium catalyst for ethylene polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453154B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749786A (en) * | 2016-07-20 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of polyethylene catalysts |
| CN108690150A (en) * | 2017-04-07 | 2018-10-23 | 中国石油化工股份有限公司 | A kind of catalyst system and olefine polymerizing process for olefinic polymerization |
| CN109160963A (en) * | 2018-08-28 | 2019-01-08 | 吉化集团吉林市天龙催化剂有限公司 | A kind of magnesium-modified chromium-based catalysts of ethylene polymerization and preparation method thereof |
| CN112409514A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
| CN114621368A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Ethylene gas-phase polymerization grade switching agent and preparation method thereof |
| CN114621371A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Method for rapidly switching gas-phase method polyethylene metallocene catalyst to chromium catalyst on line |
| CN115536767A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Supported chromium-based polyethylene catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3324095A (en) * | 1965-05-14 | 1967-06-06 | Union Carbide Corp | Polymerization process |
| CN1753729A (en) * | 2003-02-26 | 2006-03-29 | 尤尼威蒂恩技术有限责任公司 | Production of broad molecular weight polyethylene |
| CN101173013A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
-
2010
- 2010-10-22 CN CN2010105150350A patent/CN102453154B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3324095A (en) * | 1965-05-14 | 1967-06-06 | Union Carbide Corp | Polymerization process |
| CN1753729A (en) * | 2003-02-26 | 2006-03-29 | 尤尼威蒂恩技术有限责任公司 | Production of broad molecular weight polyethylene |
| CN101173013A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749786A (en) * | 2016-07-20 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of polyethylene catalysts |
| CN108690150A (en) * | 2017-04-07 | 2018-10-23 | 中国石油化工股份有限公司 | A kind of catalyst system and olefine polymerizing process for olefinic polymerization |
| CN108690150B (en) * | 2017-04-07 | 2020-11-10 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and olefin polymerization method |
| CN109160963A (en) * | 2018-08-28 | 2019-01-08 | 吉化集团吉林市天龙催化剂有限公司 | A kind of magnesium-modified chromium-based catalysts of ethylene polymerization and preparation method thereof |
| CN109160963B (en) * | 2018-08-28 | 2021-05-04 | 吉化集团吉林市天龙催化剂有限公司 | Magnesium modified chromium catalyst for ethylene polymerization and preparation method thereof |
| CN112409514A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
| CN112409514B (en) * | 2019-08-23 | 2023-04-28 | 中国石油化工股份有限公司 | Chromium-based polyethylene catalyst and preparation method thereof |
| CN114621368A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Ethylene gas-phase polymerization grade switching agent and preparation method thereof |
| CN114621371A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Method for rapidly switching gas-phase method polyethylene metallocene catalyst to chromium catalyst on line |
| CN114621371B (en) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | On-line rapid switching method from gas-phase polyethylene metallocene catalyst to chromium catalyst |
| CN114621368B (en) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | Ethylene gas phase polymerization grade switching agent and preparation method thereof |
| CN115536767A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Supported chromium-based polyethylene catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102453154B (en) | 2013-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453154B (en) | Organic chromium catalyst for ethylene polymerization and preparation method thereof | |
| CA1168218A (en) | Phosphate supported chromium catalyst | |
| EP2311562B1 (en) | Production of Broad Molecular Weight Polyethylene | |
| CN103351443B (en) | A kind of supported olefin polymerization catalyst and preparation method thereof and application | |
| US9611339B2 (en) | Supported double center hybrid polyethylene catalyst, process for preparing the same and use thereof | |
| US20150065667A1 (en) | Supported metal oxide double active center polyethylene catalyst, process for preparing the same and use thereof | |
| EP0105727A2 (en) | Hydrocarbon soluble catalyst supports and resultant polymerization catalysts | |
| CN105199021A (en) | Titanium fluoride modified load type chrome alum double-active center catalyst and preparation method thereof | |
| CN103626899A (en) | Inorganic carrier supported chrome-vanadium double-center composite catalyst as well as preparation method and application thereof | |
| CN104725533B (en) | A kind of olefin polymerization catalysis and olefine polymerizing process and polyolefin | |
| CN105111336A (en) | Electron donor of ethylene polymerization catalyst, ball-like catalyst and preparation method | |
| GB2525540A (en) | Olefin polymerization catalyst and preparation and application thereof | |
| CN103772540A (en) | Loaded chromium base catalyst, preparation method and application thereof | |
| JPS59223705A (en) | Polymerization catalyst and process | |
| CN102432711A (en) | Catalyst component for ethylene polymerization and preparation method thereof | |
| CN106467583B (en) | A kind of catalytic component, preparation method and application for vinyl polymerization | |
| CN108690150B (en) | Catalyst system for olefin polymerization and olefin polymerization method | |
| JPH03502471A (en) | Homogeneous or supported vanadium-based catalysts for the polymerization of olefins | |
| CN101565473B (en) | Catalyst component for ethylene polymerization and preparation and application thereof | |
| US20120065345A1 (en) | Supported hybrid chromium-based catalysts, processes for preparing the same, and uses thereof | |
| US20090005524A1 (en) | Catalysts for ethylene polymerization, main catalyst components thereof and process for preparing the same | |
| CN107434831B (en) | Chromium-based catalyst component, preparation method thereof and chromium-based catalyst | |
| RU2230074C1 (en) | Method of preparing catalyst and method of preparing agent reducing hydrod ynamic resistance based on polyhexene prepared using this catalyst | |
| CN101838351A (en) | Catalyst for vinyl polymerization and method for preparing same | |
| CN103509141B (en) | For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |