JPH0158202B2 - - Google Patents
Info
- Publication number
- JPH0158202B2 JPH0158202B2 JP5864579A JP5864579A JPH0158202B2 JP H0158202 B2 JPH0158202 B2 JP H0158202B2 JP 5864579 A JP5864579 A JP 5864579A JP 5864579 A JP5864579 A JP 5864579A JP H0158202 B2 JPH0158202 B2 JP H0158202B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- solvent
- zeolite
- hexane
- catalyst
- 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.)
- Expired
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 74
- 239000002904 solvent Substances 0.000 claims description 51
- 239000010457 zeolite Substances 0.000 claims description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 63
- -1 Y-type zeolite Chemical compound 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 15
- 238000000746 purification Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000004743 Polypropylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002044 hexane fraction Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
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The present invention relates to a method for purifying an olefin polymerization solvent. More specifically, the present invention relates to a method suitable for removing impurities that adversely affect olefin polymerization from a polymerization solvent. Many methods are known for polymerizing olefins in the presence of catalysts and solvents. The solvent recovered by separating the olefin polymer from the polymerization solution or decomposing the catalyst is often used again in the polymerization. However, even when olefin polymerization is performed using such a solvent that has been used once for polymerization, the expected polymerization activity may not be obtained. These include by-products during polymerization, catalyst decomposition products, reagents used for catalyst decomposition, such as alcohols, carboxylic acids, chelate compounds, etc., and products resulting from oxidation and thermal deterioration of solvents during polymerization and post-treatment. This is assumed to be due to the inclusion of various impurities. These impurities can be removed to some extent by combining various purification methods such as washing with water, distillation, and dehydration. Therefore, depending on the degree of purification, even if the solvent is reused, there will be no significant decrease in polymerization activity. It can be prevented. However, this level is not sufficient, and with repeated use, the polymerization activity eventually decreases to an unsatisfactory level. In recent years, there has been remarkable progress in high activation technology for polymerization catalysts, but while these highly active catalysts have the great advantage of being able to be used in very small quantities, they are particularly susceptible to The influence of impurities is likely to be large, and the above-mentioned disadvantages in solvent reuse are likely to occur. A decrease in polymerization activity due to the influence of impurities not only impairs the advantages of highly active catalysts and increases catalyst consumption, but also causes changes in the composition and molecular weight of the polymer, making it difficult to control product quality. It is to make it. Therefore, it has been desired to further remove trace amounts of polymerization-inhibiting impurities that could not be completely removed by conventional purification methods. Therefore, the inventors of the present invention conducted intensive studies to solve such problems, and found that
We have discovered a very effective method for purifying olefin polymerization solvents. That is, according to the present invention, there is provided a method for purifying a solvent, which comprises treating an olefin polymerization solvent consisting of a hydrocarbon with a zeolite ion-exchanged with transition metal ions. It is already known to use zeolites for the purpose of dehydration in solvents or for the purpose of removing alkyl halides in solvents (for example, JP-A-51-20791). However, even with this conventional purification method using zeolite treatment,
Although the effect of preventing a decrease in the activity of olefin polymerization is not sufficient, a significant improvement in the purification effect is observed by replacing the metal ions of zeolite with transition metal ions. In the present invention, zeolite ion-exchanged with transition metal ions is used as a solvent treatment agent. Zeolites used for ion exchange include, for example, molecular sieves 3A, 4A, and 5.
Zeolite known by trade names such as A, 10X, 13X, etc., synthetic zeolite such as Y-type zeolite,
Examples include natural zeolites such as borosite, siabasite, and mordenite. The transition metal ions to be ion-exchanged with these zeolites include titanium, vanadium, chromium,
Manganese, iron, cobalt, nickel, copper, zinc,
Yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, lanthanum, cerium, neodymium, promethium, samarium, coropium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, actinium, thorium, Examples include ions such as uranium. Among these, ions of elements or rare earth elements belonging to the fourth period or group 8 of the periodic table are particularly preferred, particularly ions of elements of the fourth period of the periodic table or rare earth elements. Methods for replacing metal ions, mainly alkali metal ions, in zeolites with these transition metal ions are already known and can be carried out by conventionally taught methods. For example, zeolite that has been pretreated such as washing with water or calcined, or zeolite that has not been pretreated is immersed in an aqueous solution of a compound containing transition metal ions and heated. After replacing the aqueous solution and repeating the same operation several times, the product may be washed with distilled water, dried, and fired. The exchange rate with transition metal ions is arbitrary, but usually 10 to 100%,
In particular, about 20 to 100% is preferable. The solvent purified with zeolite ion-exchanged with transition metal ions is an olefin polymerization solvent consisting of hydrocarbons. Such olefin polymerization solvents include, for example, aliphatic hydrocarbons such as butane, pentane, hexane, hebutane, octane, decane, dodecane, and kerosene; aliphatic hydrocarbons such as cyclopetane, methylcyclopetane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, etc. can be used. Furthermore, it is particularly effective to treat materials that have been used once or repeatedly in olefin polymerization when they are to be reused in olefin polymerization. Olefin polymerization is carried out using, for example, Ziegler-type catalysts.
This was done using a Phillips-type catalyst. More specifically, transition metal compounds such as titanium compounds, such as titanium trichloride, titanium tetrachloride, titanium compounds supported on magnesium compounds, etc.; vanadium compounds, such as vanadium tetrachloride, vanadium oxychloride, vanadium alkoxyhalides, etc. It can be applied to a solvent used in the polymerization of an olefin using an organic aluminum compound such as a trialkylaluminium, an alkylaluminium halide, etc., or a solvent used in the polymerization of an olefin using the catalyst. When applied to the solvent used in polymerization, it is applied to the solvent recovered by adding a catalytic decomposition agent such as alcohol to the polymerization solution, or by performing arbitrary operations such as steam distillation, water washing, alkaline washing, dehydration, distillation, etc. be able to. Examples of such olefin polymerization include ethylene, propylene, 1-butene, 1-
Polymerization or copolymerization of pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, etc., and polyenes with these olefins, such as butadiene, isoprene, piperylene, 1,4-hexadiene, 5-ethylidene. 2-Norbonene,
Examples include copolymerization with 5-vinyl-2-norbornene, dicyclopentadiene, and the like. In the present invention, it can be used not only to remove impurities that adversely affect olefin polymerization from the above-mentioned polymerization solvent, but also to remove -SO 3 H contained in the above-mentioned hydrocarbons and other hydrocarbon oils. , âCOOH, âOH, âNH 2 , âSH, â
CHO, -C=O, -COOR, -S-, -O-,
It can also be used for the purpose of removing specific compounds having functional groups such as halogens and unsaturated bonds. To treat a solvent with a zeolite ion-exchanged with transition metal ions, it is sufficient to simply bring the two into contact. The zeolite can be used in various forms such as powder, flakes, and granules. For example, a method of suspending and contacting the zeolite in a solvent in a batch manner, a continuous treatment method of continuously passing a solvent through a packed bed filled with the zeolite, etc. can be employed. The contact temperature between the solvent and the zeolite is arbitrary, but it is usually preferably about -50 to 150°C. The contact time also varies depending on the type and amount of supported metal, the yield of zeolite, the type and amount of impurities in the solvent, etc., but for example, when treating solvent 1 with 100 g of zeolite, it is generally 0.1 seconds. A contact time of about 5 to 5 hours is sufficient. If the performance of the zeolite deteriorates after repeated use, it can be easily regenerated by heating and firing it at a temperature of about 200 to 600°C in an atmosphere of an inert gas such as nitrogen gas or in the air. So it is reusable. Next, an example will be explained. Example 1 1 Polymerization and Post-Treatment EPDM polymerization reaction was carried out continuously using 15 stainless steel polymerization vessels equipped with stirring blades.
That is, hexane is continuously supplied as a polymerization solvent from the top of the polymerization vessel at a rate of 5 per hour. On the other hand, the polymerization liquid is continuously drawn out from the lower part of the polymerization vessel so that the polymerization liquid in the polymerization vessel is always 5%. The concentration of vanadium oxytrichloride as a catalyst in the polymerization vessel was 0.3 mmol/, and the concentration of ethylaluminum sesquichloride in the polymerization vessel was 0.3 mmol/.
Each was continuously fed into the polymerization vessel from the top of the vessel at a concentration of 2.4 mmol/each. In addition, a mixed gas of ethylene, propylene, and hydrogen (34 mol% ethylene, 56 mol% propylene, 10 mol% hydrogen) was supplied from the top of the polymerization vessel at a rate of 500 N/hour, and dicyclopentadiene was added to the polymerization vessel at a concentration of 4.3 g/hour.
Supply so that The copolymerization reaction was carried out at 35°C by circulating hot water through a jacket attached to the outside of the polymerization vessel. The extracted polymerization liquid was sent to a post-treatment system and continuously treated to obtain EPDM. That is, after removing unreacted monomer gas from the polymerization solution in a demonomer tower, methanol was added to the polymerization solution 1 to deactivate the catalyst. Next, this polymerization solution was subjected to a steam stripping treatment to obtain EPDM at a rate of 52 g per polymerization solution. That is, the polymer yield per 1 mmol of vanadium catalyst was 173 g. The physical properties of the polymer were as follows: ethylene content: 70.2 mol%, iodine number: 8.6, Mooney viscosity (ML1+4, 100°C): 46. 2 Recovery of Solvent The solvent separated from the polymer by steam stripping was continuously sent to a solvent recovery step and recovered. That is, the mixture was separated into an aqueous layer and an oil layer in a stationary drum, the oil layer was continuously extracted, and a hexane fraction was obtained by removing low-boiling components and high-boiling components in a distillation column. 3 Polymerization using recovered hexane When the hexane recovered by the above operation was dehydrated with Monocube Sieve 4A and then reused, the polymerization activity decreased. In other words, the polymerization yield under the same polymerization conditions as at the start of recycled use is 1 vanadium.
The amount was 83 g per mmol, the ethylene content was 79.1 mol%, the iodine number was 17.1, and the Mooney viscosity was 103. 4 Synthesis of zeolite for solvent purification A zeolite for solvent purification was synthesized by exchanging the sodium ions of Union Carbide Y-type zeolite (SK-40) with ferrous ions. That is, ferrous chloride was dissolved in nitrogen-substituted distilled water to prepare a 20% ferrous chloride aqueous solution. Under a nitrogen atmosphere, 1 part ferrous chloride aqueous solution was added to 100 g of SK-40, and the reaction was carried out at 60°C for 3 hours. The ferrous chloride aqueous solution was replaced with a new one and the same operation was repeated two more times. Finally, the zeolite was washed with nitrogen-substituted distilled water and calcined at 500°C for 3 hours in a nitrogen atmosphere. The exchange rate of iron was 70.0% on a sodium basis. 5 Purification of Solvent 100 g of the above zeolite for solvent purification was added to 50 g of recovered hexane and immersed in a nitrogen atmosphere for one day. 6 Polymerization with Purified Hexane EPDM was polymerized under the conditions described above using the purified hexane described above as a solvent. Polymer yield is 177/mmol vanadium
The physical properties of the g-polymer are as follows: ethylene content: 70.5 mol%;
The iodine value was 8.5 and the Mooney viscosity was 44, and both the polymerization activity and the physical properties of the polymer were equivalent to those of hexane before recycling. This indicates that the hexane was completely purified. Examples 2 to 4 The same operations as in Example 1 were repeated except that 5A, 10X, and 13X type zeolites were used instead of Y type zeolite. The results are shown in Table 1.
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çµæãè¡šïŒã«ç€ºãã[Table] Comparative Examples 1 to 4 Here, for comparison with the present invention, it is shown that zeolite before exchange with iron ions is not effective for solvent purification. The same operation as in Example 1 was performed except that instead of using zeolite exchanged with iron ions, zeolites (SK-40, 5A, 10X, 13X) before iron ion exchange were used. The results are shown in Table 2.
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çµæãè¡šïŒã«ç€ºãã[Table] Example 19 Same procedure as in Example 1 except that instead of using iron-supported Y-type zeolite as the zeolite for solvent purification, Union Carbide's Y-type zeolite (SK-500) supporting cesium and lanthanum was used. The operation was repeated. The polymer yield was 159 g/mmolV, the ethylene content of the polymer was 73.9 mol%, the iodine number was 9.5, and the Mooney viscosity was 54.
It was hot. Example 20 Here, an example of purification of a polypropylene polymerization solvent will be shown. 1 Catalyst preparation 20 g of anhydrous magnesium chloride, 4.6 ml of ethyl benzoate and 3.0 ml of methylpolysiloxane (viscosity 20 c.s. (25°C) were mixed in a nitrogen atmosphere with a diameter of 15 mm.
The balls were placed in a stainless steel (SUS-32) ball mill cylinder with an internal volume of 800 ml and an inner diameter of 100 mm containing 2.8 kg of stainless steel (SUS-32) balls and left in contact for 100 hours at an impact acceleration of 7.8 G. 10 g of the obtained solid treated product was suspended in 100 ml of titanium tetrachloride, and after contact at 80°C for 2 hours with stirring, the solid component was collected by filtration, and free titanium tetrachloride was no longer detected in the washing liquid. After washing with hexane until
It was dried to obtain a titanium-containing solid component (a). 2 Polymerization and Post-Treatment Slurry polymerization of polypropylene was carried out continuously using 15 stainless steel polymerization vessels equipped with stirring blades. That is, hexane as a polymerization solvent is continuously drawn out from the top of the polymerization vessel at a rate of 5 ml/hour so that the polymerization liquid is always 5 ml/hour.
The composite (a) as a catalyst was polymerized so that the concentration of titanium in the polymerization vessel was 1.0 mmol/, and the third component of the catalyst was methyl P-toluate so that the concentration in the polymerization vessel was 0.33 mmol/. It was continuously fed into the polymerization vessel from the middle of the vessel. In addition, 3.1 kg of propylene is supplied per hour from the top of the polymerization vessel.
Hydrogen was supplied at a rate of 8.3N per hour. The reaction was carried out at 70°C by circulating hot water through a jacket attached to the outside of the polymerization vessel. The extracted polymer solution was sent to a post-treatment system and continuously subjected to the following treatment to collect a polymer. That is, the monomer in the polymerization solution was removed in a tower and then separated into a slurry and a solvent in a decanter. A polymer was obtained at a ratio of 310 g per hexane. That is, the polymer yield per 1 mmol of titanium catalyst was 15,500 g. In addition, the melt index (MI
230â) was 10.2. 3 Recovery of solvent The mother liquor separated from the slurry was supplied to a distillation column, low boiling point components and high boiling point components were removed, and a hexane fraction was recovered. 4 Polymerization using recovered hexane When the hexane recovered by the above operation was dehydrated with Molecular Sieve 4A and reused, the polymerization activity decreased. That is, under the same polymerization conditions as at the beginning of use, the polymer yield was 5000 g/mmol titanium. 5 Purification of Solvent Hexane was purified in the same manner as in Example 1 using zeolite for solvent purification. 6 Polymerization with Purified Hexane Polypropylene was polymerized under the conditions described above using the purified hexane described above as a solvent. Polymer yield was 15,300 g/mmol titanium. Moreover, MI230°C was 10.5, and both the polymerization activity and melt index were equivalent to that of hexane before recycling. This indicates that the hexane was completely purified. Example 21 Here, an example of purification of a polyethylene polymerization solvent using a Ziegler catalyst will be described. 1 Preparation of Catalyst 2 moles of commercially available anhydrous magnesium chloride were suspended in dehydrated and purified hexane 4 under a nitrogen atmosphere, and 12 moles of ethanol was added dropwise over 2 hours with stirring, followed by reaction at 70°C for 1 hour. To this was added dropwise 5.85 mol of diethylaluminum chloride at room temperature, and the mixture was stirred for 2 hours. Subsequently, 3 mol of titanium tetrachloride was added dropwise, and the reaction was carried out at room temperature for 2 hours. After the reaction was completed, the solid portion produced was washed repeatedly with hexane to obtain a titanium-containing solid component (b). 2 Polymerization and post-treatment In Example 20, instead of using the composite (a), triethylaluminum, and methyl P-toluate as the catalyst and propylene as the monomer, the above composite (b) was used as the catalyst, and the titanium concentration in the polymerization vessel was increased.
The concentration of triethylaluminum in the polymerization vessel was 1.0 mmol/0.02 mmol/
Also, ethylene as a monomer is added per hour so that
A similar operation was performed except that 1.5Kg hydrogen was supplied at a rate of 18N/hour. The results are shown in Table 4.
Claims (1)
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ãç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã[Scope of Claims] 1. A method for purifying a solvent, which comprises treating an olefin polymerization solvent consisting of carbon and hydrogen under zeolite ion-exchanged with transition metal ions. 2. The method according to claim 1, wherein the olefin polymerization solvent is a polymerization solvent used in olefin polymerization using a transition metal compound catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5864579A JPS55151003A (en) | 1979-05-15 | 1979-05-15 | Purification of solvent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5864579A JPS55151003A (en) | 1979-05-15 | 1979-05-15 | Purification of solvent |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS55151003A JPS55151003A (en) | 1980-11-25 |
JPH0158202B2 true JPH0158202B2 (en) | 1989-12-11 |
Family
ID=13090313
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5864579A Granted JPS55151003A (en) | 1979-05-15 | 1979-05-15 | Purification of solvent |
Country Status (1)
Country | Link |
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JP (1) | JPS55151003A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP3671253B2 (en) * | 1995-07-03 | 2005-07-13 | æåé»å·¥æ ªåŒäŒç€Ÿ | Method for producing polyolefin |
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1979
- 1979-05-15 JP JP5864579A patent/JPS55151003A/en active Granted
Also Published As
Publication number | Publication date |
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JPS55151003A (en) | 1980-11-25 |
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