JPH0210695B2 - - Google Patents
Info
- Publication number
- JPH0210695B2 JPH0210695B2 JP57184668A JP18466882A JPH0210695B2 JP H0210695 B2 JPH0210695 B2 JP H0210695B2 JP 57184668 A JP57184668 A JP 57184668A JP 18466882 A JP18466882 A JP 18466882A JP H0210695 B2 JPH0210695 B2 JP H0210695B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- bismuth
- tungsten
- propylene
- molybdenum
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 106
- 239000000203 mixture Substances 0.000 claims description 41
- 229910052797 bismuth Inorganic materials 0.000 claims description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 33
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052721 tungsten Inorganic materials 0.000 claims description 25
- 239000010937 tungsten Substances 0.000 claims description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001622 bismuth compounds Chemical class 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 150000003658 tungsten compounds Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- -1 acrolein Chemical compound 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940049676 bismuth hydroxide Drugs 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- 239000005909 Kieselgur Substances 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
æ¬çºæã¯ããããã¬ã³ãååç¶é
žçŽ å«æã¬ã¹ã«
ããæ¥è§Šæ°çžé žåãããã¢ã¯ãã¬ã€ã³ããã³ã¢ã¯
ãªã«é žãããããã®è§Šåªã«é¢ããã詳ããè¿°ã¹ã
ã°ãæ¬çºæã¯ãããã¬ã³ãååç¶é žçŽ å«æã¬ã¹ã
ãšãã°ç©ºæ°ãçšããŠæ¥è§Šæ°çžé žåããã¢ã¯ãã¬ã€
ã³ããã³ã¢ã¯ãªã«é žããšãã«äž»ãšããŠã¢ã¯ãã¬ã€
ã³ãé«ãéžææ§ãã€é«ãåçã§ããããã®è§Šåªã«
é¢ãããã®ã§ãããé·æãã€å®å®ããŠå·¥æ¥çã«äœ¿
çšããã觊åªãæäŸãããã®ã§ããã ãããã¬ã³ãæ¥è§Šæ°çžé žåããŠã¢ã¯ãã¬ã€ã³ã
ãã³ã¢ã¯ãªã«é žã補é ããããã®è§Šåªã¯æ°å€ãæ
æ¡ãããŠããã ãã®ä»£è¡šäŸãšããŠã¢ãªããã³ããã³ãã¹ãã¹ã
äž»äœãšãã觊åªç³»ããããå ·äœäŸããããã°ãç¹
å ¬æ36â3563å·å ¬å ±æ现æžã«ã¯ã¢ãªããã³é žãã¹
ãã¹ããã³ãªã³ã¢ãªããã³é žãã¹ãã¹ãããªã觊
åªãç¹å ¬æ39â3670å·å ¬å ±æ现æžã«ã¯ãéããã¹
ãã¹ããªã³ããã³ã¢ãªããã³ãæ§æå çŽ ãšãã觊
åªçµæç©ãç±³åœç¹èš±ç¬¬352299å·æ现æžã«ã¯ããã
ã±ã«ãã³ãã«ããéããã¹ãã¹ãã¢ãªããã³ã«ãª
ã³ãç çŽ ãããŠçŽ ãããã«ã«ãªãŠã ãã«ããžãŠ
ã ãã»ã·ãŠã ãæ§æå çŽ ãšãã觊åªçµæç©ãé瀺
ãããŠããåŠãã§ããã ãŸããäžæ¹ã«ã¯ã¿ã³ã°ã¹ãã³ããã³ãã¹ãã¹ã
äž»äœãšãã觊åªç³»ããããç±³åœç¹èš±ç¬¬3089909å·
æ现æžã«ã¯ãã¹ãã¹ã®ã¿ã³ã°ã¹ãã³é žå¡©ãç¹å ¬æ
39â18017å·å ¬å ±æ现æžã«ã¯ãã¹ãã¹ãã³ãã«ãã
ã¿ã³ã°ã¹ãã³ç³»è§Šåªçµæåãææ¡ãããŠãããã
ãã«ã¯ãã¢ãªããã³ããã¹ãã¹ãã¿ã³ã°ã¹ãã³ã
äž»äœãšãã觊åªç³»ãææ¡ãããŠãããäŸãã°ç¹é
æ49â9490å·ãç¹éæ49â14393å·ããããç¹å ¬
æ47â42241å·å ¬å ±æ现æžã«ã¯ã¢ãªããã³ãã³ã
ã«ããéããã¹ãã¹ãã¿ã³ã°ã¹ãã³ãã±ã€çŽ ãã¢
ã«ã«ãªéå±ãæ§æå çŽ ãšãã觊åªçµæç©ãææ¡ã
ããŠããã ãããå ¬ç¥ã®ææ¡ã«ãªãå€æ°ã®è§Šåªã«ãããŠã¯
åæã®ææ¡ã®ãã®ã«ã¯ã¢ã¯ãã¬ã€ã³ããã³ã¢ã¯ãª
ã«é žã®åçã®é¢ã§å·¥æ¥ç䜿çšã«ãããŠãããŸã äž
ååãªãã®ãå€ãã€ãããè¿æã«è³ãã«ãããã
çš®ã ã®æ¹è¯ãå ããããå·¥æ¥çã«äœ¿çšå¯èœã®åã«
éãããã®ãæ£èŠãããããã«ãªã€ãã ããããªããããããã®ææ¡ã«ãªã觊åªã¯å®é
å·¥æ¥çã«äœ¿çšãããŠãããšã¯ããããã®æ现æžã®
å®æœäŸã«èšèŒãããŠããããã«ã¢ã¯ãã¬ã€ã³ãã
ã³ã¢ã¯ãªã«é žãé«éžæçãé«åçã§ããããšã¯ã§
ãããã¯ããã«äœãæ°Žæºã®å®çžŸãåããŠããã«ã
ããªãããšãäºå®ã§ãããå®éãå·¥æ¥çã«äœ¿çšã
ãå Žåãåœè©²æ¥è§Šæ°çžé žååå¿ãéåžžã«çºç±çã§
ããããã«ã觊åªå±€ã®äžã«ãããã¹ããããšãã
å±éšçç°åžžé«æž©åž¯ãçºçããŠé床ã®é žååå¿ãèµ·
ã€ããã觊åªã®å å¡«å±€é«ã倧ããããã«è§Šåªå±€äž
ã§ã®å§åã觊åªå±€ã®å ¥å£ããåºå£ã«åã€ãŠé 次å€
åããŠããããã«çæ³çãªåå¿ããããã¯ãªãã
ããšçããã®åå ãšãªã€ãŠããã®ã§ãããããŸã
äžæ¹ã¢ãªããã³ãäž»äœãšããå€æå系觊åªã«ãã
ãŠã¯ãã¢ãªããã³ãå€æ°ã®å çŽ ãšå®¹æã«åå¿ããŠ
è€éãªã¢ãªããã³ã®é¯å¡©ãçããããå質ã®è§Šåª
ãããããšãå°é£ã§ããã觊åªæ§èœã®åçŸæ§ã«é£
ç¹ããããããã觊åªçµæãå·¥æ¥çãªè§Šåªè£œé ã«
çšããå Žåã補é ãããå šãŠã®è§Šåªæ§èœãäžèšæ
ç®å®æœäŸã®åŠãé«ãæ°Žæºã瀺ãããªãããšã¯åå
çŽåŸã®ãããšããã§ããã æ¬çºæè çã¯ã¢ãªããã³ããã¹ãã¹ããã³ã¿ã³
ã°ã¹ãã³ãå«ã觊åªç³»ã§ã®ãããå·¥æ¥ç䜿çšã«ã
ããæ¬ ç¹ãå æãããªããã€å·¥æ¥ç觊åªè£œé ã®èŠ
æš¡ã«ãããŠè§Šåªæ§èœã®åçŸæ§ã«ãããã調補æ¹æ³
ãéæç 究ã®çµææ¬çºæãå®æããã«è³ã€ãã ããªãã¡ãæ¬çºæã¯ããããã¬ã³ãååç¶é žçŽ
å«æã¬ã¹ã«ããæ¥è§Šæ°çžé žåãããã¢ã¯ãã¬ã€ã³
ããã³ã¢ã¯ãªã«é žãããããã®äžè¬åŒ BiaWbFecModAeBfCgDhOx ãã ãBiã¯ãã¹ãã¹ãã¯ã¿ã³ã°ã¹ãã³ãFe
ã¯éãMoã¯ã¢ãªããã³ãã¯é žçŽ ã§ãããã¯
ããã±ã«ïŒNiïŒããã³ïŒãŸãã¯ã³ãã«ãïŒCoïŒ
ãè¡šãããã¯ã¢ã«ã«ãªéå±ãã¢ãªã«ãªåé¡éå±
ããã³ã¿ãªãŠã ãããªã矀ããéžã°ããå°ããšã
ïŒçš®ã®å çŽ ãè¡šãããã¯ãªã³ïŒïŒ°ïŒããçŽ
ïŒAsïŒããã³ããŠçŽ (B)ãããªã矀ããéžã°ããå°
ããšãïŒçš®ã®å çŽ ãè¡šããããããŠïŒ€ã¯ã±ã€çŽ
ïŒSiïŒãã¢ã«ãããŠã ïŒAlïŒããã³ãã¿ããŠã
ïŒTiïŒãããªã矀ããéžã°ããå°ããšãïŒçš®ã®å
çŽ ãè¡šããããŸãæ·»åïœãïœãïœãïœãïœ ãïœã
ïœãïœããã³ïœã¯åå çŽ ã®ååæ¯ãè¡šãããïœïŒ
12ãšãããšããïœïŒ0.1ã10.0ãïœïŒ0.5ã10.0ïŒã
ã ãïœïŒïœã¯0.01ã6.0ãšããïŒãïœïŒ0.1ã10.0ã
ïœ ïŒ2.0ã20.0ãïœïŒ0.001ã2.0ãïœïŒïŒã4.0ãã
ã³ïœïŒ0.5ã15ã®å€ããšããïœã¯åã ã®å çŽ ã®å
å䟡ã«ãã€ãŠå®ãŸãæ°å€ããšãã ã§è¡šãããã觊åªçµæç©ã補é ããã«éããŠã
Biæåã¯ãã¹ãã¹ååç©ãšã¿ã³ã°ã¹ãã³ååç©
ãšã®æ··åç©ãããããã600ã900âã®æž©åºŠã§çŒæ
åŠçããŠããããé žåç©ã®åœ¢ã§å°å ¥ããããšãç¹
城ãšãããããã¬ã³é žåçšè§Šåªçµæç©ã®è£œé æ³ã
æäŸãããã®ã§ããã æ¬çºæã®è§Šåªã«ãããç¹åŸŽã¯ããã¹ãã¹ãã¿ã³
ã°ã¹ãã³ãšããããŠå®å®ããçµåããªããããã
é·æéã«ãããåå¿ã«ãããŠããã®é«ã觊åªæ§èœ
ãç¶æããããšã§ããããã®ãã¹ãã¹ãšã¿ã³ã°ã¹
ãã³ã®å®å®ããçµåã¯ãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã
ããããã600ã900âã®é«æž©ã§åŠçããŠåœ¢æãã
ããã®ã§ããããã®ãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãšã
ããªãååç©ã«ã€ããŠã®åŠè¡çç 究ãè¿å¹Žè¡ãªã
ããããã«ãªããããšãã°ãžã€ãŒãã« ãªã ã
ã€ã¿ãªã·ã¹ïŒJournal of CatalysisïŒç¬¬31巻第
200ã208é ïŒ1973幎ïŒã§ã¯çš®ã ã®ãã¹ãã¹âã¿ã³
ã°ã¹ããŒãã®ååšãæããã«ããŠãããåœçºæè
çã®å®éšã§ããããã¯400âãè¶ããé«æž©ã§ãã
ãã¬ã³ã®é žåã«æŽ»æ§ãããããšãèªãããããã
ãã®æŽ»æ§ã®æ°Žæºã¯å·¥æ¥ç䜿çšã«ããã€ãŠã¯ãšãŠã
æºè¶³ã®ãããã®ã§ã¯ãªãããã®ãã¹ãã¹ã¿ã³ã°ã¹
ããŒããã¢ãªããã³ãéããã³ä»ã®éå±å çŽ ãšã
ãã«è€åçã«çµåããããããšã«ããç±å®å®æ§ã
è¯å¥œã§ãããäœæž©ã§è§Šåªæ§èœã«ããããã空æå
çã®é«ã觊åªçµæç©ãããããããšãå€æããã®
ã§ããããããã«ç¹éæ55â47144å·å ¬å ±æ现æž
ããã³ç¹éæ49â9490å·å ¬å ±æ现æžã®äžéšã«ãã¹
ãã¹ãšã¿ã³ã°ã¹ãã³ã®æ··åç©ãå¥ã«èª¿è£œãããã
ãæ®ãã®è§Šåªæåã«å ãããšããææ¡ããã§ã«ã
ãããŠããããã®å Žåã¯ããããããå®å®ãªãã¹
ãã¹âã¿ã³ã°ã¹ãã³ååç©ã圢æããããããªæ¡
件ã§ã®çŒæã¯è¡ãªãããŠããªãã ããã«å¯ŸããŠæ¬çºæã«ãã觊åªã¯ãã¹ãã¹ãšã¿
ã³ã°ã¹ãã³ããããããé«æž©ã§åŠçããŠãããã
ããçšããããšã«ãã調補æ³ã«ãããŠããããŠå
çŸæ§ã«ããããé«æ°Žæºã®è§ŠåªãããããåŸæ¥ã®ã
ã¹ãã¹ãšã¢ãªããã³ã®ååç©ãäž»äœãšãã觊åªç³»
ã«æ¯ããå·¥æ¥ç調補æ³ãšããŠãããããŠæå©ã§ã
ãããšãå€æãããããã«é©ãã¹ãããšã«æ¬çºæ
ã«ãããŠãã¹ãã¹ã¯å®è³ªçã«ã¿ã³ã°ã¹ãã³ãšæ¥µã
ãŠåŒ·åºã«çµåããŠãããå€æå系觊åªãšããåŸã
ã¿ã³ã°ã¹ãã³ãšã®çµåã解ããããã¹ãã¹ã®åå
ç©ãããšãã°äžé žåãã¹ãã¹ããã¹ãã¹âã¢ãªã
ããŒããªã©ã¯çæããªãããšãç·åæã®åæã®
çµææãããšãªã€ãã®ã§ãããããªãã¡æ¬çºæã«
ããã觊åªã¯ãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãšã匷åºãª
çµåãä¿ã¡ã€ã€ä»ã®è§Šåªæ§æå çŽ ãšããã«è€åç
ã«çµåãããŠãããã®ãšèªããããã®ã§ãããã
ããŠé·æéã«ããããããã¬ã³ã®é žåã«äŸããåŸ
ããã®çµåç¶æ ã«ã»ãšãã©å€åã®ãªãããšãåã
ãç·åæåæã®çµæ確èªãããã®ã§ããããã
ãæ¬çºæã«ãã補é ããã觊åªã¯åå¿æž©åºŠãåŸæ¥
ã®ãã®ã«ããã¹äœãããããšãã§ãããã€ã¢ã¯ã
ã¬ã€ã³ãšã¢ã¯ãªã«é žã®åèšåçãé«ããããšãã§
ããã®ã¿ãªããããšãã«ã¡ããªãã³ãªã©ã®æçšãª
å»è¬åã®åæãšãªãã¢ã¯ãã¬ã€ã³ã®éžææ§ãé«ã
觊åªãããããšãã§ããã®ã§ããã ãããŠæ¬çºæè ãã®ç¥èŠã«ããã°ãã®ã¢ã¯ãã¬
ã€ã³ãžã®é«éžææ§ãäžãã觊åªãšããŠã¯ããã«è§Š
åªã®åœ¢ç¶ã以äžã®åŠãç¹å®ãããã®ãæšå¥šããã
ããšãæãããšãªã€ããããªãã¡ã3.0ã10.0mm
ã®å€åŸã§é·ããå€åŸã®0.5ã2.0åã®å€åœ¢ãæãã
ã€å åŸãå€åŸã®0.1ã0.7åãšãªãããã«é·ãæ¹å
ã«éåãæãããªã³ã°ç¶è§Šåªã§ããã觊åªçµæç©
ãäžèšäžè¬åŒã§ç€ºãããã€ç¹å®ãããããšãç¹åŸŽ
ãšãããããã¬ã³é žåçšè§Šåªã§ããã ãã®ããã«æ¬çºæ觊åªã®åœ¢ç¶ãç¹å®ããããš
ã¯ã以äžã®åŠãå¹æãå¥ãããã®ã§ããããšãå€
æããŠããã (i) 觊åªã®åœ¢ç¶ãäžèšç¹å®ã«ãªããªã³ã°ç¶ã«ãã
ããšã«ããã觊åªã®å¹ŸäœåŠçè¡šé¢ç©ãå¢å€§ãã
ããã«ã€ããŠãããã¬ã³ã®è»¢åçãå¢å ããã
ã€è§ŠåªçŽ°åå ã§çæããã¢ã¯ãã¬ã€ã³ã®çŽ°åå
æ¡æ£ãè±é¢ãæ¡æ£æã®éè·¯ã®ççž®ãšãããŸã€
ãŠãåæ±ç¶ã®ãã®ã«æ¯ã¹ãŠãã¿ããã«ãªããé
次åå¿ã§ããã¢ã¯ãã¬ã€ã³ããã¢ã¯ãªã«é žãé ¢
é žãäºé žåççŽ ãäžé žåççŽ ãžã®åå¿ãäœäžã
ãã (ii) ãªã³ã°ç¶è§Šåªã«ããããšã§åœç¶äºæ³ãããã®
ã§ãããã觊åªå±€äžã§ã®å§åæ倱ãæžããå·¥æ¥
çç£ã«ãããããã¯ãŒã®é»åè²»ãäœæžããããš
ãå¯èœãšãªãã (iii) ãŸããæ¬çºæã®è§Šåªã¯è§Šåªå¯¿åœã䌞ã³ããšã
ãå©ç¹ãæããŠãããããªãã¡ãäžè¬ã«æ¥è§Šæ°
çžé žåãéåžžã«çºç±çã§ããããã«èµ·ããå±æ
ç°åžžé«æž©åž¯ã®æž©åºŠãããªã³ã°ç¶è§Šåªã«ããããš
ã«ããé€ç±å¹æã®å¢å€§ãšãå ã«è¿°ã¹ãã¢ã¯ãªã«
é žãé ¢é žãäºé žåççŽ ãäžé žåççŽ ãžã®é次å
å¿ã«ããçºç±ã®æžå°ããããŸã€ãŠããããã¹ã
ããã®æž©åºŠãäœäžããåå¿äžã«è§Šåªæåã®äžã€
ã§ããã¢ãªããã³ã®é£æ£ãåå ã§èµ·ããå§åæ
倱ã®äžæçãå°ãããªã觊åªã®å¯¿åœãã®ã°ãçµ
æãšãªãã æ¬çºæã®è§Šåªã¯äžèšäžè¬åŒã§ç€ºãããçµæç¯å²
ãããªããã®ã§ãããããã®èª¿è£œæ³ã¯äžèšããåŠ
ãç¹è³ªãå ·æããããã°ãçš®ã ã«éžã¶ããšãã§ã
ãã ãŸããã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã®çµåäœã®çææ¹
æ³ã«ã€ããŠã奜ãŸãã調補æ³ã®äžäŸã以äžã«ç€º
ãã æåã«ãã¹ãã¹ååç©ãããšãã°ç¡é žãã¹ã
ã¹ãæ°Žé žåãã¹ãã¹ãé žåãã¹ãã¹ãšã¿ã³ã°ã¹ã
ã³ã®ååç©ããšãã°ãã©ã¿ã³ã°ã¹ãã³é žã¢ã³ã¢ã
ãŠã ãé žåã¿ã³ã°ã¹ãã³ãšãå°éã®æ°Žãšå ±ã«ãã
æ··åã也ç¥åŸ600ã900âã奜ãŸããã¯700ã850â
ã®é«æž©ã§åŠçãè¡ãªãç²ç ãããç²ç ã¯å°ããã
ãæ¹ãè¯ããå¿ èŠä»¥äžã®çŽ°ç²åã¯ç¡é§ã§ããã
100ã¡ãã·ãŠä»¥äžçšåºŠã§å åã§ãããããããŠã
ã¹ãã¹âã¿ã³ã°ã¹ãã³ååç©ãããããšãã§ã
ããã€ãã§è§Šåªã調補ããäžå ·äœäŸã以äžã«ç€º
ãããããããã¢ãªããã³ã®ååç©ããšãã°ã¢ãª
ããã³é žã¢ã³ã¢ããŠã ã®æ°Žæº¶æ¶²ã«éã®ååç©ããš
ãã°ç¡é žéã®æ°Žæº¶æ¶²ãå ããäžè¬åŒäžã§ç€ºããã
ã®å çŽ ãšããŠã³ãã«ããçšããå Žåã¯ããšãã°
ç¡é žã³ãã«ãã®æ°Žæº¶æ¶²ãããšããŠã¢ã«ã«ãªéå±
ãçšããå Žåã¯ã¢ã«ã«ãªéå±æºãšããŠã¢ã«ã«ãªé
å±æ°Žé žåç©ãããã¯ç¡é žå¡©ãããšããŠãªã³ãçš
ããå Žåã¯ãªã³é žæ°Žæº¶æ¶²ãããšããŠã±ã€çŽ ãçš
ããå Žåã¯ã³ãã€ãã«ã·ãªã«çãçšã氎溶液ãã
ãæ··åããããããæ³¥ç¶ç©ã«å¯Ÿããå ã®ç²ç ãã
ããã¹ãã¹ã¿ã³ã°ã¹ãã³ã®çµåç©ãæ·»å ãããã
ã«ããæ··åããŠæ¿çž®ããããããç²åç¶ç©è³ªãæ
圢åŸ350âã650âã奜ãŸããã¯400âã600âã®æž©
床ã§ç©ºæ°æµéäžã«ãŠçŒæãå®æ觊åªãããã ãªããå¿ èŠã«å¿ããŠç²æ«ç¶ã®æ äœç©è³ªãåèšæ³¥
ç¶ç©äžã«æ·»å ããŠäœ¿çšããããšãã§ããã æ äœãšããŠã¯ãã·ãªã«ã²ã«ãã¢ã«ãããã·ãªã³
ã³ã«ãŒãã€ããã±ã€è»åãé žåãã¿ã³ããã³ã»ã©
ã€ãïŒåååïŒãªã©ããéžã°ããããšãã«ã·ãªã«
ã²ã«ãé žåãã¿ã³ãã»ã©ã€ããé©åœã§ããã æ¬è§Šåªã®ç¹åŸŽã§ãããã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã®
é žçŽ å«æååç©ã¯ãã¹ãã¹ã®ã¿ã³ã°ã¹ãã³ã«å¯Ÿã
ãååæ¯ã0.01ã6.0ã奜ãŸããã¯0.1ã4.0ã®ç¯å²
ã«éå®ããããããªãã¡ã6.0ãè¶ããååæ¯ã®
ãã¹ãã¹âã¿ã³ã°ã¹ãã³ååç©ã¯å®å®ãªçµåç¶æ
ããšãããã觊åªèª¿è£œäžãããã¯è§Šåªã®é·æ䜿çš
äžã«ãã¹ãã¹ã¿ã³ã°ã¹ãã³ã®çµåãããããã¹ã
ã¹ãä»ã®æåãšåçµåããŠã觊åªã®åæåã®çµå
ãã©ã³ã¹ã厩ãã奜ãŸããçµæããããããªãã
ãã§ããããã¡ãããã®ãããªååæ¯ãæºè¶³ãã
ãšåæã«é«æž©åŠçæ¡ä»¶ãå¿ é ã®èŠä»¶ã§ããããã¹
ãã¹ãšã¿ã³ã°ã¹ãã³ã®é žçŽ å«æååç©ã¯ãã®ãã
ãªæž©åºŠç¯å²ã§ã®åŠçã«ãã€ãŠå®å®ãªååç©ã圢æ
ãããããæ¬çºæã®è§Šåªçµæç©äžã«çµã¿èŸŒãŸãã
ããšã«ãã€ãŠãã®è§Šåªæ§èœãããããŠé«æ°Žæºã«åŒ
ãäžããã600âã«æºããªãäœæž©éšã§ã®ãã¹ãã¹
ãšã¿ã³ã°ã¹ãã³ãšã®ååç©ã®ç±åŠçã¯ãããšãã
ã®ååæ¯ãäžèšç¯å²ãæºè¶³ãããã®ã§ãã€ãŠã觊
åªçµæç©äžã§å®å®åããã觊åªèª¿è£œäžãããã¯è§Š
åªã®äœ¿çšäžã«ã觊åªçµæç©ã«ãããçµåãã©ã³ã¹
ã厩ããåå ãšãªã奜ãŸãããªãããŸã900âã
è¶ããé«æž©ã§ã®åŠçããã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãš
ã®å®å®ãªçµåäœããã«ããã觊åªçµæç©äžã«ãã
ãŠå€åãããããã奜ãŸããã¯ãªãã æ¬çºæã«ããã觊åªåæãšããŠã¯ãäžèšã®åå
ç©ã«éå®ããããã®ã§ã¯ãªãããã¹ãã¹ããã³ã¿
ã³ã°ã¹ãã³ã«é¢ããŠã¯å¡©åãã¹ãã¹ãªã©ã®ããã²
ã³åãã¹ãã¹ãçé žãã¹ãã¹ãéçé žãã¹ãã¹ã
æ°Žé žåãã¹ãã¹ãé ¢é žãã¹ãã¹ãªã©ã®ææ©é žãã¹
ãã¹å¡©ãã¿ã³ã°ã¹ãã³é žãããªãŠã ãªã©ã®ã¿ã³ã°
ã¹ãã³é žã®ã¢ã«ã«ãªéå±å¡©ãå¡©åã¿ã³ã°ã¹ãã³é¡
ãªã©ã®ããã²ã³åã¿ã³ã°ã¹ãã³é¡ãªã©ãé©å®äœ¿çš
ããããããã²ã³åç©ãã¢ã«ã«ãªå¡©ã䜿çšããå Ž
åã¯ã¹ã©ãªãŒãéããåŸååãªæŽæ»ãå¿ èŠã§ã
ãããšã¯ãããŸã§ããªãã ã¢ãªããã³ãéããã³ãã®ä»ã®è§Šåªåæã«ã€ã
ãŠããç¡é žå¡©ãææ©é žå¡©ã¯å¿è«ã®ããšè§Šåªèª¿è£œã«
åã ã®é žåç©ã圢æããããã®ã§ããã°ãããªã
ååç©ã§ã䜿çšå¯èœã§ããããã¡ããäžèšè§Šåªã
æ§æããå çŽ ã®ïŒçš®ãªããïŒçš®ãå«æããååç©
ãåæ§ã«äœ¿çšãããã ãããŠã觊åªã®èª¿è£œæ¹æ³ãšããŠããäžèšã®ã»ã
ã«è§Šåªçµæç©äžã®å觊åªæåãåäžã«æ··åãããŠ
ååšãããæ¹æ³ã§ããã°ããããªãæ¹æ³ã§ãæ¡çš
ããããšãã§ããããšãã°ãã¹ãã¹ãšã¿ã³ã°ã¹ã
ã³ã®èª¿è£œãããç²æ«ããç²æ«åãããã³ãã«ãã
éãã¢ãªããã³ãã±ã€çŽ ããã³ã¢ã«ã«ãªéå±ã®é ž
åç©æ··åç©ãšãšãã«æ··åããçŒæã«ãã€ãŠæ¶æ» ã
ãã«ã«ããã·ã¡ãã«ã»ã«ããŒã¹ãªã©ã®çµåå€ãæ·»
å ããŠåäžã«æ··ç·Žãäžèšãšåæ§ã«ããŠææã®è§Šåª
çµæç©ãããããšãã§ããã ãã®ããã«ããŠãããã觊åªãçšããŠ250ã450
âã®åå¿æž©åºŠãåžžå§ã10æ°å§ã®å§åäžãïŒã12容
éïŒ ã®ãããã¬ã³ãïŒã18容éïŒ ã®é žçŽ ãïŒã60
容éïŒ ã®æ°Žèžæ°ããã³20ã50容éïŒ ã®çªçŽ ã¬ã¹ã
çé žã¬ã¹ãªã©ã®äžæŽ»æ§ã¬ã¹ãããªãåæã¬ã¹ãæ¥
觊æé1.0ã10.0ç§ã§åå¿ããããã ãŸããæ¬çºæã«ãã觊åªã¯åºå®åºåŒåå¿ã«ãã
ãŠãæµååºåŒåå¿ã«ãããŠã䜿çšã§ãããã®ã§ã
ãã®éžæããåœæ¥è ãé©å®è¡ãªããããšããã§ã
ãã 以äžãå®æœäŸãæ¯èŒäŸã瀺ãæ¬çºæãããã«è©³
现ã«èª¬æããããæ¬çºæã¯ãã®äž»æšã«åããªãã
ãã以äžã®å®æœäŸã«éå®ããããã®ã§ã¯ãªãã ãªããæ¬çºæã«ãããåå¿çãéžæçããã³å
æµåçã以äžã®ããã«å®çŸ©ãããã®ãšããã åå¿çïŒã¢ã«ïŒ ïŒ ïŒåå¿ãããããã¬ã³ã®ã¢ã«æ°ïŒäŸçµŠãããããã¬
ã³ã®ã¢ã«æ°Ã100 éžæçïŒã¢ã«ïŒ ïŒïŒçæããã¢ã¯ãã¬ã€ã³ãŸãã¯ã¢
ã¯ãªã«é žã®ã¢ã«æ°ïŒåå¿ãããããã¬ã³ã®ã¢ã«æ°Ã100 åæµåçïŒã¢ã«ïŒ ïŒïŒçæããã¢ã¯ãã¬ã€ã³ãŸãã¯
ã¢ã¯ãªã«é žã®ã¢ã«æ°ïŒäŸçµŠãããããã¬ã³ã®ã¢ã«æ°Ã10
0 å®æœäŸ ïŒ ç¡é žãã¹ãã¹486ïœããæ¿ç¡é ž104mlãå ããŠé ž
æ§ãšããèžçæ°Ž1000mlã«æº¶è§£ããããã®æ°Žæº¶æ¶²
ã«ãã¢ã³ã¢ãã¢æ°ŽïŒ28ïŒ ïŒ1100mlãå ãçœè²æ²æ®¿
ç©ãããããããå¥æ°ŽæŽããããããçœè²ã±ãŒ
ãç¶ç©è³ªã«ã464ïœã®äžé žåã¿ã³ã°ã¹ãã³ãå ã
å åæ··åããã®ã¡ã230âã§16æé也ç¥ãããã
ãã«ç©ºæ°æµéäž750âã§ïŒæéç±åŠçãè¡ãªã€ãã
ããããé»è²å¡ç¶ç©ã100ã¡ãã·ãŠä»¥äžã«ç²ç ã
é»è²ç²äœãããããã®ç²äœãç·åç·åæãããš
ããå ã®æç®ã«ç€ºãããŠããïœïŒ2.973ã3.207ã
2.706ã1.648ã1.915ã«ããŒã¯ã®ããBi2ïŒWO4ïŒ3ãš
ïœïŒ3.632ã3.817ã3.739ã2.610ã«ããŒã¯ã®ãã
WO3ã®æ··åç©ã§ãããé žåãã¹ãã¹ã®ããŒã¯ã¯
å šãèªããããªãããšãåã€ãã å¥ã«ã¢ãªããã³é žã¢ã³ã¢ããŠã 766ïœãèžçæ°Ž
8000mlã«æº¶è§£ãã氎溶液ã«ãç¡é žã³ãã«ã1164ïœ
ã800mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ãç¡é žç¬¬ïŒé
118ïœã400mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ã20éé
ïŒ ã®ã·ãªã«ãå«ãã·ãªã«ãŸã«400ïœããã³ç¡é žã«
ãªãŠã 5.1ïœã100mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ã
ããããå ãã宀枩äžæ¹æããã ããããæžæ¿æ¶²ãå ç±æ¿çž®ããã也ç¥ããã®ã¡
ç²ç ããããã®ç²äœã«å ã®é»è²ç²äœãå ãååæ··
åããã®ã¡èžçæ°Žãå ããŠããæ··ç·ŽããçŽåŸ5.5
mmãé·ãïŒmmã®ãã¬ããç¶ã«æåã也ç¥åŸç©ºæ°æµ
éäž450âã§ïŒæéçŒæããŠå®æ觊åªãšããã ãã®è§Šåªã®é žçŽ ãã®ããçµæã¯ååæ¯ã§ Bi1.2W2.4Fe0.35Mo12Co4.8K0.06Si1.6 ã§ãã€ãïŒä»¥äžåæ§ã«è§Šåªçµæãè¡šçŸãããïŒãã§
ãããã€ã觊åªãç·åæåæãããšããå ã®ã
ã¹ãã¹ã¿ã³ã°ã¹ããŒãã®ããŒã¯ã¯ãã®ãŸãŸèªãã
ããã¹ãã¹ãé žçŽ ä»¥å€ã®ä»ã®å çŽ ãšçµåãããã
ãšãã°ãã¹ãã¹ã¢ãªãããŒããªã©ã«é¢ããããŒã¯
ã¯å šãèªããããªãã€ãã ããããŠãããã觊åªã®ãã¡1520mlãå åŸ25.4
mmÏã®éŒé補åå¿ç®¡ã«å±€é·3000mmã§å å¡«ããå€éš
ã®ç±åªïŒæº¶èå¡©ïŒæž©åºŠã295âã«å ç±ããããã
ã¬ã³ïŒå®¹éïŒ ãé žçŽ 12.6容éïŒ ãæ°Žèžæ°10.0容é
ïŒ ãçªçŽ 70.4容éïŒ ãããªãçµæã®åæã¬ã¹ãå°
å ¥ãæ¥è§Šæé2.0ç§ïŒNTPæç®ïŒã§åå¿ããã第
ïŒè¡šã«ç€ºãçµæãããã ãªããåæã¯ã¬ã¹ã¯ãããã°ã©ãã€ãŒããã³é ž
滎å®æ³ã§è¡ãªã€ãã ãã®è§Šåªã§5000æéåå¿ãè¡ãªã€ãåŸãæãåº
ããŠïŒžç·åæãè¡ãªã€ããšããã䜿çšåã®è§Šåªãš
å€åã¯èªããããªãã€ãã æ¯èŒäŸ ïŒ å®æœäŸïŒã«ãããŠãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãšã®
é«æž©åŠçç©ãçšããªãã»ãã¯åæ§ã«ããŠè¡ããäž
èšã®çµæã®è§Šåªã調補ããã Fe0.35Mo12Co4.8K0.06Si1.6 ãããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶äžã§åå¿ã
è¡šïŒã«ç€ºãçµæãããã æ¯èŒäŸ ïŒ å®æœäŸïŒã«ãããŠäžé žåã¿ã³ã°ã¹ãã³ãçšããª
ãã»ãã¯åæ§ã«è¡ãªãäžèšã®çµæã®è§Šåªã調補ã
ãã Bi1.2Fe0.35Mo12Co4.8K0.06Si1.6 ãããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶ã§åå¿ãè¡š
ïŒã«ç€ºãçµæãããã æ¯èŒäŸ ïŒ å®æœäŸïŒã«ãããŠãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã
500âã§ïŒæéç±åŠçããŠè¡ãªã€ã以å€ã¯åæ§ã«
è¡ãªããå®æœäŸïŒã«ããã觊åªãšåãçµæã®è§Šåª
ãããããããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶äžã§
åå¿ãè¡šïŒã«ç€ºãçµæãããã å®æœäŸ ïŒ ç¡é žãã¹ãã¹405ïœããæ¿ç¡é ž80mlãå ããŠé ž
æ§ãšããèžçæ°Ž920mlã«æº¶è§£ã80âã«å ç±ããã
ã¿ã³ã°ã¹ãã³é žãããªãŠã 138ïœã1700mlã®æ°Žã«
溶解ããç¡é žã§PHã2.2ã«èª¿æŽããã®ã¡80âã«å
ç±ããäžèšç¡é žãã¹ãã¹æº¶æ¶²ã«æ¹æäžã«æ·»å ã
ããããããçœè²æ²æ®¿ç©ãå¥ãããããªãŠã ã€
ãªã³ãæ€åºãããªããªããŸã§æ°ŽæŽããããããã
çœè²ã±ãŒããå®æœäŸïŒã«ããããšåæ§ã«åŠçãé»
è²ç²äœãããã å¥ã«ã¢ãªããã³é žã¢ã³ã¢ããŠã 1766ïœã8000ml
ã®èžçæ°Žã«æº¶è§£ãã氎溶液ã«ãç¡é žã³ãã«ã970
ïœã800mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ãç¡é žç¬¬ïŒ
é336ïœã1000mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ã20
ééïŒ ã®ã·ãªã«ãå«ãã·ãªã«ãŸã«400ïœããã³ç¡
é žã«ãªãŠã 5.1ïœã100mlã®èžçæ°Žã«æº¶è§£ãã氎溶
液ãããããå ã宀枩äžæ¹æããã ããããæžæ¿æ¶²ã«æ¿ç¡é ž90mlããã³ç¡é žã¢ã³ã¢
ããŠã 600ïœãå ããåŸãäžèšé»è²ç²äœãå ãã
å ç±æ¹æäžã«æ¿çž®ããããå®æœäŸïŒã«ããããšå
æ§ã«æå也ç¥åŸç©ºæ°æµéäž450âã§ïŒæéçŒæã
äžèšçµæã®è§Šåªãããã Bi1W0.5Fe1Mo12Co4K0.06Si1.6 ãããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶äžã§åå¿
ããè¡šïŒã«ç€ºãçµæãããã å®æœäŸ ïŒ å®æœäŸïŒã®è§Šåªãçšãé«æ¿åºŠã®ãããã¬ã³ãšç©º
æ°ãæ°Žèžæ°ãçšããŠåå¿ãè¡ãªã€ãŠè¡šïŒã«ç€ºãçµ
æãããã å®æœäŸ ïŒãïŒ å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šïŒäžã«ç€ºã
çµæã®è§Šåªã調補ããããããã¬ã³ã®é žååå¿æ¡
件ããã³çµæã¯è¡šïŒã®éãã§ããã çšããåæã¯ããã±ã«ãã¿ãªãŠã ãããªãŠã ã
ã¹ããã³ããŠã ãã«ã«ã·ãŠã ãã¢ã«ãããŠã æºãš
ããŠã¯ããããã®ç¡é žå¡©ãã«ããžãŠã æºãšããŠã¯
æ°Žé žåã«ããžãŠã ãããã¿ããŠã æºãšããŠã¯äºé ž
åãã¿ããŠã ãããªã³æºãšããŠã¯ãªã³é žããããŠ
çŽ æºãšããŠã¯ããŠé žãããããçšããã å®æœäŸ 10 å®æœäŸïŒãšåãçµæåã³èª¿è£œæ³ã«ãã觊åªãå€
åŸ6.0mmãé·ã6.6mmãç©ŽåŸ1.0mmã®ãªã³ã°ç¶ã«æå
ãå®æœäŸïŒãšåæ§ã®åå¿ãè¡ãªãè¡šïŒã«ç€ºãçµæ
ãããã å®æœäŸ 11 ã¢ãªããã³é žã¢ã³ã¢ããŠã 1766ïœãèžçæ°Ž8000
mlã«æº¶è§£ãã氎溶液ã«ãç¡é žã³ãã«ã970ïœã800
mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ãå ããå®æœäŸïŒã§
調補ããé»è²ç²äœããã³æ¿ç¡é ž90mlãå ããåŸã
ç¡é žç¬¬ïŒé336ïœã1000mlã®èžçæ°Žã«æº¶è§£ããæ°Ž
溶液ã20ééïŒ ã®ã·ãªã«ãå«ãã·ãªã«ãŸã«400ïœã
ç¡é žã«ãªãŠã 5.1ïœã100mlã®èžçæ°Žã«æº¶è§£ããæ°Ž
溶液ããã³ç¡é žã¢ã³ã¢ããŠã 600ïœãããããå
ã宀枩äžæ¹æããã ãã®æžæ¿æ¶²ãã¹ãã¬ãŒãã©ã€ã€ãŒã§ä¹Ÿç¥ããŠåŸ
ãããç²äœã«èžçæ°Žãå ããŠããæ··ç·Žããå€åŸïŒ
mmãé·ã6.6mmãç©ŽåŸ2.0mmã®ãªã³ã°ç¶ã«æåãå®
æœäŸïŒãšåæ§ã®ç±åŠçãæœããåå¿ãããšããè¡š
ïŒã«ç€ºãçµæãåŸãã
ããæ¥è§Šæ°çžé žåãããã¢ã¯ãã¬ã€ã³ããã³ã¢ã¯
ãªã«é žãããããã®è§Šåªã«é¢ããã詳ããè¿°ã¹ã
ã°ãæ¬çºæã¯ãããã¬ã³ãååç¶é žçŽ å«æã¬ã¹ã
ãšãã°ç©ºæ°ãçšããŠæ¥è§Šæ°çžé žåããã¢ã¯ãã¬ã€
ã³ããã³ã¢ã¯ãªã«é žããšãã«äž»ãšããŠã¢ã¯ãã¬ã€
ã³ãé«ãéžææ§ãã€é«ãåçã§ããããã®è§Šåªã«
é¢ãããã®ã§ãããé·æãã€å®å®ããŠå·¥æ¥çã«äœ¿
çšããã觊åªãæäŸãããã®ã§ããã ãããã¬ã³ãæ¥è§Šæ°çžé žåããŠã¢ã¯ãã¬ã€ã³ã
ãã³ã¢ã¯ãªã«é žã補é ããããã®è§Šåªã¯æ°å€ãæ
æ¡ãããŠããã ãã®ä»£è¡šäŸãšããŠã¢ãªããã³ããã³ãã¹ãã¹ã
äž»äœãšãã觊åªç³»ããããå ·äœäŸããããã°ãç¹
å ¬æ36â3563å·å ¬å ±æ现æžã«ã¯ã¢ãªããã³é žãã¹
ãã¹ããã³ãªã³ã¢ãªããã³é žãã¹ãã¹ãããªã觊
åªãç¹å ¬æ39â3670å·å ¬å ±æ现æžã«ã¯ãéããã¹
ãã¹ããªã³ããã³ã¢ãªããã³ãæ§æå çŽ ãšãã觊
åªçµæç©ãç±³åœç¹èš±ç¬¬352299å·æ现æžã«ã¯ããã
ã±ã«ãã³ãã«ããéããã¹ãã¹ãã¢ãªããã³ã«ãª
ã³ãç çŽ ãããŠçŽ ãããã«ã«ãªãŠã ãã«ããžãŠ
ã ãã»ã·ãŠã ãæ§æå çŽ ãšãã觊åªçµæç©ãé瀺
ãããŠããåŠãã§ããã ãŸããäžæ¹ã«ã¯ã¿ã³ã°ã¹ãã³ããã³ãã¹ãã¹ã
äž»äœãšãã觊åªç³»ããããç±³åœç¹èš±ç¬¬3089909å·
æ现æžã«ã¯ãã¹ãã¹ã®ã¿ã³ã°ã¹ãã³é žå¡©ãç¹å ¬æ
39â18017å·å ¬å ±æ现æžã«ã¯ãã¹ãã¹ãã³ãã«ãã
ã¿ã³ã°ã¹ãã³ç³»è§Šåªçµæåãææ¡ãããŠãããã
ãã«ã¯ãã¢ãªããã³ããã¹ãã¹ãã¿ã³ã°ã¹ãã³ã
äž»äœãšãã觊åªç³»ãææ¡ãããŠãããäŸãã°ç¹é
æ49â9490å·ãç¹éæ49â14393å·ããããç¹å ¬
æ47â42241å·å ¬å ±æ现æžã«ã¯ã¢ãªããã³ãã³ã
ã«ããéããã¹ãã¹ãã¿ã³ã°ã¹ãã³ãã±ã€çŽ ãã¢
ã«ã«ãªéå±ãæ§æå çŽ ãšãã觊åªçµæç©ãææ¡ã
ããŠããã ãããå ¬ç¥ã®ææ¡ã«ãªãå€æ°ã®è§Šåªã«ãããŠã¯
åæã®ææ¡ã®ãã®ã«ã¯ã¢ã¯ãã¬ã€ã³ããã³ã¢ã¯ãª
ã«é žã®åçã®é¢ã§å·¥æ¥ç䜿çšã«ãããŠãããŸã äž
ååãªãã®ãå€ãã€ãããè¿æã«è³ãã«ãããã
çš®ã ã®æ¹è¯ãå ããããå·¥æ¥çã«äœ¿çšå¯èœã®åã«
éãããã®ãæ£èŠãããããã«ãªã€ãã ããããªããããããã®ææ¡ã«ãªã觊åªã¯å®é
å·¥æ¥çã«äœ¿çšãããŠãããšã¯ããããã®æ现æžã®
å®æœäŸã«èšèŒãããŠããããã«ã¢ã¯ãã¬ã€ã³ãã
ã³ã¢ã¯ãªã«é žãé«éžæçãé«åçã§ããããšã¯ã§
ãããã¯ããã«äœãæ°Žæºã®å®çžŸãåããŠããã«ã
ããªãããšãäºå®ã§ãããå®éãå·¥æ¥çã«äœ¿çšã
ãå Žåãåœè©²æ¥è§Šæ°çžé žååå¿ãéåžžã«çºç±çã§
ããããã«ã觊åªå±€ã®äžã«ãããã¹ããããšãã
å±éšçç°åžžé«æž©åž¯ãçºçããŠé床ã®é žååå¿ãèµ·
ã€ããã觊åªã®å å¡«å±€é«ã倧ããããã«è§Šåªå±€äž
ã§ã®å§åã觊åªå±€ã®å ¥å£ããåºå£ã«åã€ãŠé 次å€
åããŠããããã«çæ³çãªåå¿ããããã¯ãªãã
ããšçããã®åå ãšãªã€ãŠããã®ã§ãããããŸã
äžæ¹ã¢ãªããã³ãäž»äœãšããå€æå系觊åªã«ãã
ãŠã¯ãã¢ãªããã³ãå€æ°ã®å çŽ ãšå®¹æã«åå¿ããŠ
è€éãªã¢ãªããã³ã®é¯å¡©ãçããããå質ã®è§Šåª
ãããããšãå°é£ã§ããã觊åªæ§èœã®åçŸæ§ã«é£
ç¹ããããããã觊åªçµæãå·¥æ¥çãªè§Šåªè£œé ã«
çšããå Žåã補é ãããå šãŠã®è§Šåªæ§èœãäžèšæ
ç®å®æœäŸã®åŠãé«ãæ°Žæºã瀺ãããªãããšã¯åå
çŽåŸã®ãããšããã§ããã æ¬çºæè çã¯ã¢ãªããã³ããã¹ãã¹ããã³ã¿ã³
ã°ã¹ãã³ãå«ã觊åªç³»ã§ã®ãããå·¥æ¥ç䜿çšã«ã
ããæ¬ ç¹ãå æãããªããã€å·¥æ¥ç觊åªè£œé ã®èŠ
æš¡ã«ãããŠè§Šåªæ§èœã®åçŸæ§ã«ãããã調補æ¹æ³
ãéæç 究ã®çµææ¬çºæãå®æããã«è³ã€ãã ããªãã¡ãæ¬çºæã¯ããããã¬ã³ãååç¶é žçŽ
å«æã¬ã¹ã«ããæ¥è§Šæ°çžé žåãããã¢ã¯ãã¬ã€ã³
ããã³ã¢ã¯ãªã«é žãããããã®äžè¬åŒ BiaWbFecModAeBfCgDhOx ãã ãBiã¯ãã¹ãã¹ãã¯ã¿ã³ã°ã¹ãã³ãFe
ã¯éãMoã¯ã¢ãªããã³ãã¯é žçŽ ã§ãããã¯
ããã±ã«ïŒNiïŒããã³ïŒãŸãã¯ã³ãã«ãïŒCoïŒ
ãè¡šãããã¯ã¢ã«ã«ãªéå±ãã¢ãªã«ãªåé¡éå±
ããã³ã¿ãªãŠã ãããªã矀ããéžã°ããå°ããšã
ïŒçš®ã®å çŽ ãè¡šãããã¯ãªã³ïŒïŒ°ïŒããçŽ
ïŒAsïŒããã³ããŠçŽ (B)ãããªã矀ããéžã°ããå°
ããšãïŒçš®ã®å çŽ ãè¡šããããããŠïŒ€ã¯ã±ã€çŽ
ïŒSiïŒãã¢ã«ãããŠã ïŒAlïŒããã³ãã¿ããŠã
ïŒTiïŒãããªã矀ããéžã°ããå°ããšãïŒçš®ã®å
çŽ ãè¡šããããŸãæ·»åïœãïœãïœãïœãïœ ãïœã
ïœãïœããã³ïœã¯åå çŽ ã®ååæ¯ãè¡šãããïœïŒ
12ãšãããšããïœïŒ0.1ã10.0ãïœïŒ0.5ã10.0ïŒã
ã ãïœïŒïœã¯0.01ã6.0ãšããïŒãïœïŒ0.1ã10.0ã
ïœ ïŒ2.0ã20.0ãïœïŒ0.001ã2.0ãïœïŒïŒã4.0ãã
ã³ïœïŒ0.5ã15ã®å€ããšããïœã¯åã ã®å çŽ ã®å
å䟡ã«ãã€ãŠå®ãŸãæ°å€ããšãã ã§è¡šãããã觊åªçµæç©ã補é ããã«éããŠã
Biæåã¯ãã¹ãã¹ååç©ãšã¿ã³ã°ã¹ãã³ååç©
ãšã®æ··åç©ãããããã600ã900âã®æž©åºŠã§çŒæ
åŠçããŠããããé žåç©ã®åœ¢ã§å°å ¥ããããšãç¹
城ãšãããããã¬ã³é žåçšè§Šåªçµæç©ã®è£œé æ³ã
æäŸãããã®ã§ããã æ¬çºæã®è§Šåªã«ãããç¹åŸŽã¯ããã¹ãã¹ãã¿ã³
ã°ã¹ãã³ãšããããŠå®å®ããçµåããªããããã
é·æéã«ãããåå¿ã«ãããŠããã®é«ã觊åªæ§èœ
ãç¶æããããšã§ããããã®ãã¹ãã¹ãšã¿ã³ã°ã¹
ãã³ã®å®å®ããçµåã¯ãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã
ããããã600ã900âã®é«æž©ã§åŠçããŠåœ¢æãã
ããã®ã§ããããã®ãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãšã
ããªãååç©ã«ã€ããŠã®åŠè¡çç 究ãè¿å¹Žè¡ãªã
ããããã«ãªããããšãã°ãžã€ãŒãã« ãªã ã
ã€ã¿ãªã·ã¹ïŒJournal of CatalysisïŒç¬¬31巻第
200ã208é ïŒ1973幎ïŒã§ã¯çš®ã ã®ãã¹ãã¹âã¿ã³
ã°ã¹ããŒãã®ååšãæããã«ããŠãããåœçºæè
çã®å®éšã§ããããã¯400âãè¶ããé«æž©ã§ãã
ãã¬ã³ã®é žåã«æŽ»æ§ãããããšãèªãããããã
ãã®æŽ»æ§ã®æ°Žæºã¯å·¥æ¥ç䜿çšã«ããã€ãŠã¯ãšãŠã
æºè¶³ã®ãããã®ã§ã¯ãªãããã®ãã¹ãã¹ã¿ã³ã°ã¹
ããŒããã¢ãªããã³ãéããã³ä»ã®éå±å çŽ ãšã
ãã«è€åçã«çµåããããããšã«ããç±å®å®æ§ã
è¯å¥œã§ãããäœæž©ã§è§Šåªæ§èœã«ããããã空æå
çã®é«ã觊åªçµæç©ãããããããšãå€æããã®
ã§ããããããã«ç¹éæ55â47144å·å ¬å ±æ现æž
ããã³ç¹éæ49â9490å·å ¬å ±æ现æžã®äžéšã«ãã¹
ãã¹ãšã¿ã³ã°ã¹ãã³ã®æ··åç©ãå¥ã«èª¿è£œãããã
ãæ®ãã®è§Šåªæåã«å ãããšããææ¡ããã§ã«ã
ãããŠããããã®å Žåã¯ããããããå®å®ãªãã¹
ãã¹âã¿ã³ã°ã¹ãã³ååç©ã圢æããããããªæ¡
件ã§ã®çŒæã¯è¡ãªãããŠããªãã ããã«å¯ŸããŠæ¬çºæã«ãã觊åªã¯ãã¹ãã¹ãšã¿
ã³ã°ã¹ãã³ããããããé«æž©ã§åŠçããŠãããã
ããçšããããšã«ãã調補æ³ã«ãããŠããããŠå
çŸæ§ã«ããããé«æ°Žæºã®è§ŠåªãããããåŸæ¥ã®ã
ã¹ãã¹ãšã¢ãªããã³ã®ååç©ãäž»äœãšãã觊åªç³»
ã«æ¯ããå·¥æ¥ç調補æ³ãšããŠãããããŠæå©ã§ã
ãããšãå€æãããããã«é©ãã¹ãããšã«æ¬çºæ
ã«ãããŠãã¹ãã¹ã¯å®è³ªçã«ã¿ã³ã°ã¹ãã³ãšæ¥µã
ãŠåŒ·åºã«çµåããŠãããå€æå系觊åªãšããåŸã
ã¿ã³ã°ã¹ãã³ãšã®çµåã解ããããã¹ãã¹ã®åå
ç©ãããšãã°äžé žåãã¹ãã¹ããã¹ãã¹âã¢ãªã
ããŒããªã©ã¯çæããªãããšãç·åæã®åæã®
çµææãããšãªã€ãã®ã§ãããããªãã¡æ¬çºæã«
ããã觊åªã¯ãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãšã匷åºãª
çµåãä¿ã¡ã€ã€ä»ã®è§Šåªæ§æå çŽ ãšããã«è€åç
ã«çµåãããŠãããã®ãšèªããããã®ã§ãããã
ããŠé·æéã«ããããããã¬ã³ã®é žåã«äŸããåŸ
ããã®çµåç¶æ ã«ã»ãšãã©å€åã®ãªãããšãåã
ãç·åæåæã®çµæ確èªãããã®ã§ããããã
ãæ¬çºæã«ãã補é ããã觊åªã¯åå¿æž©åºŠãåŸæ¥
ã®ãã®ã«ããã¹äœãããããšãã§ãããã€ã¢ã¯ã
ã¬ã€ã³ãšã¢ã¯ãªã«é žã®åèšåçãé«ããããšãã§
ããã®ã¿ãªããããšãã«ã¡ããªãã³ãªã©ã®æçšãª
å»è¬åã®åæãšãªãã¢ã¯ãã¬ã€ã³ã®éžææ§ãé«ã
觊åªãããããšãã§ããã®ã§ããã ãããŠæ¬çºæè ãã®ç¥èŠã«ããã°ãã®ã¢ã¯ãã¬
ã€ã³ãžã®é«éžææ§ãäžãã觊åªãšããŠã¯ããã«è§Š
åªã®åœ¢ç¶ã以äžã®åŠãç¹å®ãããã®ãæšå¥šããã
ããšãæãããšãªã€ããããªãã¡ã3.0ã10.0mm
ã®å€åŸã§é·ããå€åŸã®0.5ã2.0åã®å€åœ¢ãæãã
ã€å åŸãå€åŸã®0.1ã0.7åãšãªãããã«é·ãæ¹å
ã«éåãæãããªã³ã°ç¶è§Šåªã§ããã觊åªçµæç©
ãäžèšäžè¬åŒã§ç€ºãããã€ç¹å®ãããããšãç¹åŸŽ
ãšãããããã¬ã³é žåçšè§Šåªã§ããã ãã®ããã«æ¬çºæ觊åªã®åœ¢ç¶ãç¹å®ããããš
ã¯ã以äžã®åŠãå¹æãå¥ãããã®ã§ããããšãå€
æããŠããã (i) 觊åªã®åœ¢ç¶ãäžèšç¹å®ã«ãªããªã³ã°ç¶ã«ãã
ããšã«ããã觊åªã®å¹ŸäœåŠçè¡šé¢ç©ãå¢å€§ãã
ããã«ã€ããŠãããã¬ã³ã®è»¢åçãå¢å ããã
ã€è§ŠåªçŽ°åå ã§çæããã¢ã¯ãã¬ã€ã³ã®çŽ°åå
æ¡æ£ãè±é¢ãæ¡æ£æã®éè·¯ã®ççž®ãšãããŸã€
ãŠãåæ±ç¶ã®ãã®ã«æ¯ã¹ãŠãã¿ããã«ãªããé
次åå¿ã§ããã¢ã¯ãã¬ã€ã³ããã¢ã¯ãªã«é žãé ¢
é žãäºé žåççŽ ãäžé žåççŽ ãžã®åå¿ãäœäžã
ãã (ii) ãªã³ã°ç¶è§Šåªã«ããããšã§åœç¶äºæ³ãããã®
ã§ãããã觊åªå±€äžã§ã®å§åæ倱ãæžããå·¥æ¥
çç£ã«ãããããã¯ãŒã®é»åè²»ãäœæžããããš
ãå¯èœãšãªãã (iii) ãŸããæ¬çºæã®è§Šåªã¯è§Šåªå¯¿åœã䌞ã³ããšã
ãå©ç¹ãæããŠãããããªãã¡ãäžè¬ã«æ¥è§Šæ°
çžé žåãéåžžã«çºç±çã§ããããã«èµ·ããå±æ
ç°åžžé«æž©åž¯ã®æž©åºŠãããªã³ã°ç¶è§Šåªã«ããããš
ã«ããé€ç±å¹æã®å¢å€§ãšãå ã«è¿°ã¹ãã¢ã¯ãªã«
é žãé ¢é žãäºé žåççŽ ãäžé žåççŽ ãžã®é次å
å¿ã«ããçºç±ã®æžå°ããããŸã€ãŠããããã¹ã
ããã®æž©åºŠãäœäžããåå¿äžã«è§Šåªæåã®äžã€
ã§ããã¢ãªããã³ã®é£æ£ãåå ã§èµ·ããå§åæ
倱ã®äžæçãå°ãããªã觊åªã®å¯¿åœãã®ã°ãçµ
æãšãªãã æ¬çºæã®è§Šåªã¯äžèšäžè¬åŒã§ç€ºãããçµæç¯å²
ãããªããã®ã§ãããããã®èª¿è£œæ³ã¯äžèšããåŠ
ãç¹è³ªãå ·æããããã°ãçš®ã ã«éžã¶ããšãã§ã
ãã ãŸããã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã®çµåäœã®çææ¹
æ³ã«ã€ããŠã奜ãŸãã調補æ³ã®äžäŸã以äžã«ç€º
ãã æåã«ãã¹ãã¹ååç©ãããšãã°ç¡é žãã¹ã
ã¹ãæ°Žé žåãã¹ãã¹ãé žåãã¹ãã¹ãšã¿ã³ã°ã¹ã
ã³ã®ååç©ããšãã°ãã©ã¿ã³ã°ã¹ãã³é žã¢ã³ã¢ã
ãŠã ãé žåã¿ã³ã°ã¹ãã³ãšãå°éã®æ°Žãšå ±ã«ãã
æ··åã也ç¥åŸ600ã900âã奜ãŸããã¯700ã850â
ã®é«æž©ã§åŠçãè¡ãªãç²ç ãããç²ç ã¯å°ããã
ãæ¹ãè¯ããå¿ èŠä»¥äžã®çŽ°ç²åã¯ç¡é§ã§ããã
100ã¡ãã·ãŠä»¥äžçšåºŠã§å åã§ãããããããŠã
ã¹ãã¹âã¿ã³ã°ã¹ãã³ååç©ãããããšãã§ã
ããã€ãã§è§Šåªã調補ããäžå ·äœäŸã以äžã«ç€º
ãããããããã¢ãªããã³ã®ååç©ããšãã°ã¢ãª
ããã³é žã¢ã³ã¢ããŠã ã®æ°Žæº¶æ¶²ã«éã®ååç©ããš
ãã°ç¡é žéã®æ°Žæº¶æ¶²ãå ããäžè¬åŒäžã§ç€ºããã
ã®å çŽ ãšããŠã³ãã«ããçšããå Žåã¯ããšãã°
ç¡é žã³ãã«ãã®æ°Žæº¶æ¶²ãããšããŠã¢ã«ã«ãªéå±
ãçšããå Žåã¯ã¢ã«ã«ãªéå±æºãšããŠã¢ã«ã«ãªé
å±æ°Žé žåç©ãããã¯ç¡é žå¡©ãããšããŠãªã³ãçš
ããå Žåã¯ãªã³é žæ°Žæº¶æ¶²ãããšããŠã±ã€çŽ ãçš
ããå Žåã¯ã³ãã€ãã«ã·ãªã«çãçšã氎溶液ãã
ãæ··åããããããæ³¥ç¶ç©ã«å¯Ÿããå ã®ç²ç ãã
ããã¹ãã¹ã¿ã³ã°ã¹ãã³ã®çµåç©ãæ·»å ãããã
ã«ããæ··åããŠæ¿çž®ããããããç²åç¶ç©è³ªãæ
圢åŸ350âã650âã奜ãŸããã¯400âã600âã®æž©
床ã§ç©ºæ°æµéäžã«ãŠçŒæãå®æ觊åªãããã ãªããå¿ èŠã«å¿ããŠç²æ«ç¶ã®æ äœç©è³ªãåèšæ³¥
ç¶ç©äžã«æ·»å ããŠäœ¿çšããããšãã§ããã æ äœãšããŠã¯ãã·ãªã«ã²ã«ãã¢ã«ãããã·ãªã³
ã³ã«ãŒãã€ããã±ã€è»åãé žåãã¿ã³ããã³ã»ã©
ã€ãïŒåååïŒãªã©ããéžã°ããããšãã«ã·ãªã«
ã²ã«ãé žåãã¿ã³ãã»ã©ã€ããé©åœã§ããã æ¬è§Šåªã®ç¹åŸŽã§ãããã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã®
é žçŽ å«æååç©ã¯ãã¹ãã¹ã®ã¿ã³ã°ã¹ãã³ã«å¯Ÿã
ãååæ¯ã0.01ã6.0ã奜ãŸããã¯0.1ã4.0ã®ç¯å²
ã«éå®ããããããªãã¡ã6.0ãè¶ããååæ¯ã®
ãã¹ãã¹âã¿ã³ã°ã¹ãã³ååç©ã¯å®å®ãªçµåç¶æ
ããšãããã觊åªèª¿è£œäžãããã¯è§Šåªã®é·æ䜿çš
äžã«ãã¹ãã¹ã¿ã³ã°ã¹ãã³ã®çµåãããããã¹ã
ã¹ãä»ã®æåãšåçµåããŠã觊åªã®åæåã®çµå
ãã©ã³ã¹ã厩ãã奜ãŸããçµæããããããªãã
ãã§ããããã¡ãããã®ãããªååæ¯ãæºè¶³ãã
ãšåæã«é«æž©åŠçæ¡ä»¶ãå¿ é ã®èŠä»¶ã§ããããã¹
ãã¹ãšã¿ã³ã°ã¹ãã³ã®é žçŽ å«æååç©ã¯ãã®ãã
ãªæž©åºŠç¯å²ã§ã®åŠçã«ãã€ãŠå®å®ãªååç©ã圢æ
ãããããæ¬çºæã®è§Šåªçµæç©äžã«çµã¿èŸŒãŸãã
ããšã«ãã€ãŠãã®è§Šåªæ§èœãããããŠé«æ°Žæºã«åŒ
ãäžããã600âã«æºããªãäœæž©éšã§ã®ãã¹ãã¹
ãšã¿ã³ã°ã¹ãã³ãšã®ååç©ã®ç±åŠçã¯ãããšãã
ã®ååæ¯ãäžèšç¯å²ãæºè¶³ãããã®ã§ãã€ãŠã觊
åªçµæç©äžã§å®å®åããã觊åªèª¿è£œäžãããã¯è§Š
åªã®äœ¿çšäžã«ã觊åªçµæç©ã«ãããçµåãã©ã³ã¹
ã厩ããåå ãšãªã奜ãŸãããªãããŸã900âã
è¶ããé«æž©ã§ã®åŠçããã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãš
ã®å®å®ãªçµåäœããã«ããã觊åªçµæç©äžã«ãã
ãŠå€åãããããã奜ãŸããã¯ãªãã æ¬çºæã«ããã觊åªåæãšããŠã¯ãäžèšã®åå
ç©ã«éå®ããããã®ã§ã¯ãªãããã¹ãã¹ããã³ã¿
ã³ã°ã¹ãã³ã«é¢ããŠã¯å¡©åãã¹ãã¹ãªã©ã®ããã²
ã³åãã¹ãã¹ãçé žãã¹ãã¹ãéçé žãã¹ãã¹ã
æ°Žé žåãã¹ãã¹ãé ¢é žãã¹ãã¹ãªã©ã®ææ©é žãã¹
ãã¹å¡©ãã¿ã³ã°ã¹ãã³é žãããªãŠã ãªã©ã®ã¿ã³ã°
ã¹ãã³é žã®ã¢ã«ã«ãªéå±å¡©ãå¡©åã¿ã³ã°ã¹ãã³é¡
ãªã©ã®ããã²ã³åã¿ã³ã°ã¹ãã³é¡ãªã©ãé©å®äœ¿çš
ããããããã²ã³åç©ãã¢ã«ã«ãªå¡©ã䜿çšããå Ž
åã¯ã¹ã©ãªãŒãéããåŸååãªæŽæ»ãå¿ èŠã§ã
ãããšã¯ãããŸã§ããªãã ã¢ãªããã³ãéããã³ãã®ä»ã®è§Šåªåæã«ã€ã
ãŠããç¡é žå¡©ãææ©é žå¡©ã¯å¿è«ã®ããšè§Šåªèª¿è£œã«
åã ã®é žåç©ã圢æããããã®ã§ããã°ãããªã
ååç©ã§ã䜿çšå¯èœã§ããããã¡ããäžèšè§Šåªã
æ§æããå çŽ ã®ïŒçš®ãªããïŒçš®ãå«æããååç©
ãåæ§ã«äœ¿çšãããã ãããŠã觊åªã®èª¿è£œæ¹æ³ãšããŠããäžèšã®ã»ã
ã«è§Šåªçµæç©äžã®å觊åªæåãåäžã«æ··åãããŠ
ååšãããæ¹æ³ã§ããã°ããããªãæ¹æ³ã§ãæ¡çš
ããããšãã§ããããšãã°ãã¹ãã¹ãšã¿ã³ã°ã¹ã
ã³ã®èª¿è£œãããç²æ«ããç²æ«åãããã³ãã«ãã
éãã¢ãªããã³ãã±ã€çŽ ããã³ã¢ã«ã«ãªéå±ã®é ž
åç©æ··åç©ãšãšãã«æ··åããçŒæã«ãã€ãŠæ¶æ» ã
ãã«ã«ããã·ã¡ãã«ã»ã«ããŒã¹ãªã©ã®çµåå€ãæ·»
å ããŠåäžã«æ··ç·Žãäžèšãšåæ§ã«ããŠææã®è§Šåª
çµæç©ãããããšãã§ããã ãã®ããã«ããŠãããã觊åªãçšããŠ250ã450
âã®åå¿æž©åºŠãåžžå§ã10æ°å§ã®å§åäžãïŒã12容
éïŒ ã®ãããã¬ã³ãïŒã18容éïŒ ã®é žçŽ ãïŒã60
容éïŒ ã®æ°Žèžæ°ããã³20ã50容éïŒ ã®çªçŽ ã¬ã¹ã
çé žã¬ã¹ãªã©ã®äžæŽ»æ§ã¬ã¹ãããªãåæã¬ã¹ãæ¥
觊æé1.0ã10.0ç§ã§åå¿ããããã ãŸããæ¬çºæã«ãã觊åªã¯åºå®åºåŒåå¿ã«ãã
ãŠãæµååºåŒåå¿ã«ãããŠã䜿çšã§ãããã®ã§ã
ãã®éžæããåœæ¥è ãé©å®è¡ãªããããšããã§ã
ãã 以äžãå®æœäŸãæ¯èŒäŸã瀺ãæ¬çºæãããã«è©³
现ã«èª¬æããããæ¬çºæã¯ãã®äž»æšã«åããªãã
ãã以äžã®å®æœäŸã«éå®ããããã®ã§ã¯ãªãã ãªããæ¬çºæã«ãããåå¿çãéžæçããã³å
æµåçã以äžã®ããã«å®çŸ©ãããã®ãšããã åå¿çïŒã¢ã«ïŒ ïŒ ïŒåå¿ãããããã¬ã³ã®ã¢ã«æ°ïŒäŸçµŠãããããã¬
ã³ã®ã¢ã«æ°Ã100 éžæçïŒã¢ã«ïŒ ïŒïŒçæããã¢ã¯ãã¬ã€ã³ãŸãã¯ã¢
ã¯ãªã«é žã®ã¢ã«æ°ïŒåå¿ãããããã¬ã³ã®ã¢ã«æ°Ã100 åæµåçïŒã¢ã«ïŒ ïŒïŒçæããã¢ã¯ãã¬ã€ã³ãŸãã¯
ã¢ã¯ãªã«é žã®ã¢ã«æ°ïŒäŸçµŠãããããã¬ã³ã®ã¢ã«æ°Ã10
0 å®æœäŸ ïŒ ç¡é žãã¹ãã¹486ïœããæ¿ç¡é ž104mlãå ããŠé ž
æ§ãšããèžçæ°Ž1000mlã«æº¶è§£ããããã®æ°Žæº¶æ¶²
ã«ãã¢ã³ã¢ãã¢æ°ŽïŒ28ïŒ ïŒ1100mlãå ãçœè²æ²æ®¿
ç©ãããããããå¥æ°ŽæŽããããããçœè²ã±ãŒ
ãç¶ç©è³ªã«ã464ïœã®äžé žåã¿ã³ã°ã¹ãã³ãå ã
å åæ··åããã®ã¡ã230âã§16æé也ç¥ãããã
ãã«ç©ºæ°æµéäž750âã§ïŒæéç±åŠçãè¡ãªã€ãã
ããããé»è²å¡ç¶ç©ã100ã¡ãã·ãŠä»¥äžã«ç²ç ã
é»è²ç²äœãããããã®ç²äœãç·åç·åæãããš
ããå ã®æç®ã«ç€ºãããŠããïœïŒ2.973ã3.207ã
2.706ã1.648ã1.915ã«ããŒã¯ã®ããBi2ïŒWO4ïŒ3ãš
ïœïŒ3.632ã3.817ã3.739ã2.610ã«ããŒã¯ã®ãã
WO3ã®æ··åç©ã§ãããé žåãã¹ãã¹ã®ããŒã¯ã¯
å šãèªããããªãããšãåã€ãã å¥ã«ã¢ãªããã³é žã¢ã³ã¢ããŠã 766ïœãèžçæ°Ž
8000mlã«æº¶è§£ãã氎溶液ã«ãç¡é žã³ãã«ã1164ïœ
ã800mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ãç¡é žç¬¬ïŒé
118ïœã400mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ã20éé
ïŒ ã®ã·ãªã«ãå«ãã·ãªã«ãŸã«400ïœããã³ç¡é žã«
ãªãŠã 5.1ïœã100mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ã
ããããå ãã宀枩äžæ¹æããã ããããæžæ¿æ¶²ãå ç±æ¿çž®ããã也ç¥ããã®ã¡
ç²ç ããããã®ç²äœã«å ã®é»è²ç²äœãå ãååæ··
åããã®ã¡èžçæ°Žãå ããŠããæ··ç·ŽããçŽåŸ5.5
mmãé·ãïŒmmã®ãã¬ããç¶ã«æåã也ç¥åŸç©ºæ°æµ
éäž450âã§ïŒæéçŒæããŠå®æ觊åªãšããã ãã®è§Šåªã®é žçŽ ãã®ããçµæã¯ååæ¯ã§ Bi1.2W2.4Fe0.35Mo12Co4.8K0.06Si1.6 ã§ãã€ãïŒä»¥äžåæ§ã«è§Šåªçµæãè¡šçŸãããïŒãã§
ãããã€ã觊åªãç·åæåæãããšããå ã®ã
ã¹ãã¹ã¿ã³ã°ã¹ããŒãã®ããŒã¯ã¯ãã®ãŸãŸèªãã
ããã¹ãã¹ãé žçŽ ä»¥å€ã®ä»ã®å çŽ ãšçµåãããã
ãšãã°ãã¹ãã¹ã¢ãªãããŒããªã©ã«é¢ããããŒã¯
ã¯å šãèªããããªãã€ãã ããããŠãããã觊åªã®ãã¡1520mlãå åŸ25.4
mmÏã®éŒé補åå¿ç®¡ã«å±€é·3000mmã§å å¡«ããå€éš
ã®ç±åªïŒæº¶èå¡©ïŒæž©åºŠã295âã«å ç±ããããã
ã¬ã³ïŒå®¹éïŒ ãé žçŽ 12.6容éïŒ ãæ°Žèžæ°10.0容é
ïŒ ãçªçŽ 70.4容éïŒ ãããªãçµæã®åæã¬ã¹ãå°
å ¥ãæ¥è§Šæé2.0ç§ïŒNTPæç®ïŒã§åå¿ããã第
ïŒè¡šã«ç€ºãçµæãããã ãªããåæã¯ã¬ã¹ã¯ãããã°ã©ãã€ãŒããã³é ž
滎å®æ³ã§è¡ãªã€ãã ãã®è§Šåªã§5000æéåå¿ãè¡ãªã€ãåŸãæãåº
ããŠïŒžç·åæãè¡ãªã€ããšããã䜿çšåã®è§Šåªãš
å€åã¯èªããããªãã€ãã æ¯èŒäŸ ïŒ å®æœäŸïŒã«ãããŠãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ãšã®
é«æž©åŠçç©ãçšããªãã»ãã¯åæ§ã«ããŠè¡ããäž
èšã®çµæã®è§Šåªã調補ããã Fe0.35Mo12Co4.8K0.06Si1.6 ãããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶äžã§åå¿ã
è¡šïŒã«ç€ºãçµæãããã æ¯èŒäŸ ïŒ å®æœäŸïŒã«ãããŠäžé žåã¿ã³ã°ã¹ãã³ãçšããª
ãã»ãã¯åæ§ã«è¡ãªãäžèšã®çµæã®è§Šåªã調補ã
ãã Bi1.2Fe0.35Mo12Co4.8K0.06Si1.6 ãããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶ã§åå¿ãè¡š
ïŒã«ç€ºãçµæãããã æ¯èŒäŸ ïŒ å®æœäŸïŒã«ãããŠãã¹ãã¹ãšã¿ã³ã°ã¹ãã³ã
500âã§ïŒæéç±åŠçããŠè¡ãªã€ã以å€ã¯åæ§ã«
è¡ãªããå®æœäŸïŒã«ããã觊åªãšåãçµæã®è§Šåª
ãããããããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶äžã§
åå¿ãè¡šïŒã«ç€ºãçµæãããã å®æœäŸ ïŒ ç¡é žãã¹ãã¹405ïœããæ¿ç¡é ž80mlãå ããŠé ž
æ§ãšããèžçæ°Ž920mlã«æº¶è§£ã80âã«å ç±ããã
ã¿ã³ã°ã¹ãã³é žãããªãŠã 138ïœã1700mlã®æ°Žã«
溶解ããç¡é žã§PHã2.2ã«èª¿æŽããã®ã¡80âã«å
ç±ããäžèšç¡é žãã¹ãã¹æº¶æ¶²ã«æ¹æäžã«æ·»å ã
ããããããçœè²æ²æ®¿ç©ãå¥ãããããªãŠã ã€
ãªã³ãæ€åºãããªããªããŸã§æ°ŽæŽããããããã
çœè²ã±ãŒããå®æœäŸïŒã«ããããšåæ§ã«åŠçãé»
è²ç²äœãããã å¥ã«ã¢ãªããã³é žã¢ã³ã¢ããŠã 1766ïœã8000ml
ã®èžçæ°Žã«æº¶è§£ãã氎溶液ã«ãç¡é žã³ãã«ã970
ïœã800mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ãç¡é žç¬¬ïŒ
é336ïœã1000mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ã20
ééïŒ ã®ã·ãªã«ãå«ãã·ãªã«ãŸã«400ïœããã³ç¡
é žã«ãªãŠã 5.1ïœã100mlã®èžçæ°Žã«æº¶è§£ãã氎溶
液ãããããå ã宀枩äžæ¹æããã ããããæžæ¿æ¶²ã«æ¿ç¡é ž90mlããã³ç¡é žã¢ã³ã¢
ããŠã 600ïœãå ããåŸãäžèšé»è²ç²äœãå ãã
å ç±æ¹æäžã«æ¿çž®ããããå®æœäŸïŒã«ããããšå
æ§ã«æå也ç¥åŸç©ºæ°æµéäž450âã§ïŒæéçŒæã
äžèšçµæã®è§Šåªãããã Bi1W0.5Fe1Mo12Co4K0.06Si1.6 ãããã觊åªãå®æœäŸïŒãšåãæ¡ä»¶äžã§åå¿
ããè¡šïŒã«ç€ºãçµæãããã å®æœäŸ ïŒ å®æœäŸïŒã®è§Šåªãçšãé«æ¿åºŠã®ãããã¬ã³ãšç©º
æ°ãæ°Žèžæ°ãçšããŠåå¿ãè¡ãªã€ãŠè¡šïŒã«ç€ºãçµ
æãããã å®æœäŸ ïŒãïŒ å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šïŒäžã«ç€ºã
çµæã®è§Šåªã調補ããããããã¬ã³ã®é žååå¿æ¡
件ããã³çµæã¯è¡šïŒã®éãã§ããã çšããåæã¯ããã±ã«ãã¿ãªãŠã ãããªãŠã ã
ã¹ããã³ããŠã ãã«ã«ã·ãŠã ãã¢ã«ãããŠã æºãš
ããŠã¯ããããã®ç¡é žå¡©ãã«ããžãŠã æºãšããŠã¯
æ°Žé žåã«ããžãŠã ãããã¿ããŠã æºãšããŠã¯äºé ž
åãã¿ããŠã ãããªã³æºãšããŠã¯ãªã³é žããããŠ
çŽ æºãšããŠã¯ããŠé žãããããçšããã å®æœäŸ 10 å®æœäŸïŒãšåãçµæåã³èª¿è£œæ³ã«ãã觊åªãå€
åŸ6.0mmãé·ã6.6mmãç©ŽåŸ1.0mmã®ãªã³ã°ç¶ã«æå
ãå®æœäŸïŒãšåæ§ã®åå¿ãè¡ãªãè¡šïŒã«ç€ºãçµæ
ãããã å®æœäŸ 11 ã¢ãªããã³é žã¢ã³ã¢ããŠã 1766ïœãèžçæ°Ž8000
mlã«æº¶è§£ãã氎溶液ã«ãç¡é žã³ãã«ã970ïœã800
mlã®èžçæ°Žã«æº¶è§£ãã氎溶液ãå ããå®æœäŸïŒã§
調補ããé»è²ç²äœããã³æ¿ç¡é ž90mlãå ããåŸã
ç¡é žç¬¬ïŒé336ïœã1000mlã®èžçæ°Žã«æº¶è§£ããæ°Ž
溶液ã20ééïŒ ã®ã·ãªã«ãå«ãã·ãªã«ãŸã«400ïœã
ç¡é žã«ãªãŠã 5.1ïœã100mlã®èžçæ°Žã«æº¶è§£ããæ°Ž
溶液ããã³ç¡é žã¢ã³ã¢ããŠã 600ïœãããããå
ã宀枩äžæ¹æããã ãã®æžæ¿æ¶²ãã¹ãã¬ãŒãã©ã€ã€ãŒã§ä¹Ÿç¥ããŠåŸ
ãããç²äœã«èžçæ°Žãå ããŠããæ··ç·Žããå€åŸïŒ
mmãé·ã6.6mmãç©ŽåŸ2.0mmã®ãªã³ã°ç¶ã«æåãå®
æœäŸïŒãšåæ§ã®ç±åŠçãæœããåå¿ãããšããè¡š
ïŒã«ç€ºãçµæãåŸãã
ãè¡šã
ãè¡šã
ãè¡šã
ãè¡šã
å®æœäŸ 12
å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ããçµæã®è§Šåªã調補ããããã ãæå也ç¥åŸ
ã«ç©ºæ°æµéäž525âã§ïŒæéçŒæãããçšããå
æã¯ããã±ã«ããã°ãã·ãŠã ãã¿ãªãŠã ã¯ããã
ãã®ç¡é žå¡©ãããªã³æºãšããŠã¯ãªã³é žãçšããã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã å®æœäŸ 13ã18 å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ããçµæã®è§Šåªã調補ãããçšããåæã¯ãªã
ãŠã ã¯æ°Žé žåãªããŠã ããããªãŠã ãã¿ãªãŠã ã
ãã°ãã·ãŠã ã¯ããããã®ç¡é žå¡©ãããªã³æºã¯ãª
ã³é žãã¢ã«ãããŠã æºãšããŠã¯é žåã¢ã«ãããŠ
ã ããã¿ããŠã æºãšããŠã¯äºé žåãã¿ã³ãããã
ã䜿çšããã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã å®æœäŸ 19 å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ããçµæã®è§Šåªã調補ããããã ããçŽ åæãš
ããŠã¯äºãé žã䜿çšããããã±ã«æºãšããŠã¯ç¡é ž
ããã±ã«ã䜿çšãããåãçŒæã¯ç©ºæ°æµéäž500
âã§ïŒæéè¡ã€ãã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã å®æœäŸ 20 å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ãçµæã®è§Šåªã調補ããããã ãçŒæ枩床ã¯
480âã§è¡ã€ãã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã
瀺ããçµæã®è§Šåªã調補ããããã ãæå也ç¥åŸ
ã«ç©ºæ°æµéäž525âã§ïŒæéçŒæãããçšããå
æã¯ããã±ã«ããã°ãã·ãŠã ãã¿ãªãŠã ã¯ããã
ãã®ç¡é žå¡©ãããªã³æºãšããŠã¯ãªã³é žãçšããã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã å®æœäŸ 13ã18 å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ããçµæã®è§Šåªã調補ãããçšããåæã¯ãªã
ãŠã ã¯æ°Žé žåãªããŠã ããããªãŠã ãã¿ãªãŠã ã
ãã°ãã·ãŠã ã¯ããããã®ç¡é žå¡©ãããªã³æºã¯ãª
ã³é žãã¢ã«ãããŠã æºãšããŠã¯é žåã¢ã«ãããŠ
ã ããã¿ããŠã æºãšããŠã¯äºé žåãã¿ã³ãããã
ã䜿çšããã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã å®æœäŸ 19 å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ããçµæã®è§Šåªã調補ããããã ããçŽ åæãš
ããŠã¯äºãé žã䜿çšããããã±ã«æºãšããŠã¯ç¡é ž
ããã±ã«ã䜿çšãããåãçŒæã¯ç©ºæ°æµéäž500
âã§ïŒæéè¡ã€ãã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã å®æœäŸ 20 å®æœäŸïŒã«ããããšåæ§ã®æ¹æ³ã§è¡šâïŒ(4)äžã«
瀺ãçµæã®è§Šåªã調補ããããã ãçŒæ枩床ã¯
480âã§è¡ã€ãã ãããã¬ã³ã®é žååå¿ã®æ¡ä»¶ããã³çµæãè¡šâ
ïŒ(4)ã«ç€ºãã
ãè¡šã
Claims (1)
- ãç¹èš±è«æ±ã®ç¯å²ã ïŒ ãããã¬ã³ãååç¶é žçŽ å«æã¬ã¹ã«ããæ¥è§Š
æ°çžé žåãããã¢ã¯ãã¬ã€ã³ããã³ã¢ã¯ãªã«é žã
ããããã®äžè¬åŒ BiaWbFecModAeBfCgDhOx ãã ãBiã¯ãã¹ãã¹ãã¯ã¿ã³ã°ã¹ãã³ãFe
ã¯éãMoã¯ã¢ãªããã³ãã¯é žçŽ ã§ãããã¯
ããã±ã«ïŒNiïŒããã³ïŒãŸãã¯ã³ãã«ãïŒCoïŒ
ãè¡šãããã¯ã¢ã«ã«ãªéå±ãã¢ãªã«ãªåé¡éå±
ããã³ã¿ãªãŠã ãããªã矀ããéžã°ããå°ããšã
ïŒçš®ã®å çŽ ãè¡šãããã¯ãªã³ïŒïŒ°ïŒããçŽ
ïŒAsïŒããã³ããŠçŽ (B)ãããªã矀ããéžã°ããå°
ããšãïŒçš®ã®å çŽ ãè¡šããããããŠïŒ€ã¯ã±ã€çŽ
ïŒSiïŒãã¢ã«ãããŠã ïŒAlïŒããã³ãã¿ããŠã
ïŒTiïŒãããªã矀ããéžã°ããå°ããšãïŒçš®ã®å
çŽ ãè¡šããããŸãæ·»åïœãïœãïœãïœãïœ ãïœã
ïœãïœããã³ïœã¯åå çŽ ã®ååæ¯ãè¡šãããïœïŒ
12ãšãããšããïœïŒ0.1ã10.0ãïœïŒ0.5ã10.0ïŒã
ã ãïœïŒïœã¯0.01ã6.0ãšããïŒãïœïŒ0.1ã10.0ã
ïœ ïŒ2.0ã20.0ãïœïŒ0.001ã2.0ãïœïŒïŒã4.0ãã
ã³ïœïŒ0.5ã15ã®å€ããšããïœã¯åã ã®å çŽ ã®å
å䟡ã«ãã€ãŠå®ãŸãæ°å€ããšãã ã§è¡šãããã觊åªçµæç©ã補é ããã«éããŠã
Biæåã¯ãã¹ãã¹ååç©ãšã¿ã³ã°ã¹ãã³ååç©
ãšã®æ··åç©ãããããã600ã900âã®æž©åºŠã§çŒæ
åŠçããŠããããé žåç©ã®åœ¢ã§å°å ¥ããããšãç¹
城ãšãããããã¬ã³é žåçšè§Šåªçµæç©ã®è£œé æ³ã
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57184668A JPS5976541A (ja) | 1982-10-22 | 1982-10-22 | ãããã¬ã³é žåçšè§Šåªã®è£œé æ³ |
US06/543,150 US4537874A (en) | 1982-10-22 | 1983-10-18 | Catalyst for production of unsaturated aldehydes |
DE19833338380 DE3338380A1 (de) | 1982-10-22 | 1983-10-21 | Katalysator zur herstellung von ungesaettigten aldehyden |
FR8316871A FR2534904B1 (fr) | 1982-10-22 | 1983-10-24 | Catalyseur pour la fabrication d'aldehydes insatures |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57184668A JPS5976541A (ja) | 1982-10-22 | 1982-10-22 | ãããã¬ã³é žåçšè§Šåªã®è£œé æ³ |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5976541A JPS5976541A (ja) | 1984-05-01 |
JPH0210695B2 true JPH0210695B2 (ja) | 1990-03-09 |
Family
ID=16157264
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57184668A Granted JPS5976541A (ja) | 1982-10-22 | 1982-10-22 | ãããã¬ã³é žåçšè§Šåªã®è£œé æ³ |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5976541A (ja) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH067924B2 (ja) * | 1987-02-17 | 1994-02-02 | æ ªåŒäŒç€Ÿæ¥æ¬è§Šåª | ãããã¬ã³é žåçšè§Šåªããã³åçŸæ§ã«åªãããã®è£œé æ¹æ³ |
US4812522A (en) * | 1987-12-04 | 1989-03-14 | Shell Oil Company | Molecularly miscible blends of polyketone with polyvinyl phenol |
JP2547128B2 (ja) * | 1991-05-10 | 1996-10-23 | ã·ãŒã±ãŒãã£æ ªåŒäŒç€Ÿ | ã¹ããŒã«åŒåæåŒã«çšããå è£ ãã€ãã®è£œé æ¹æ³ |
MY121878A (en) * | 1999-03-10 | 2006-02-28 | Basf Ag | Method for the catalytic gas-phase oxidation of propene into acrylic acid |
ZA200200049B (en) | 2001-01-25 | 2002-07-16 | Nippon Catalytic Chem Ind | Fixed-bed shell-and-tube reactor and its usage. |
EP2343123B1 (en) | 2001-11-08 | 2021-01-06 | Mitsubishi Chemical Corporation | METHOD FOR PREPARATION of a COMPOSITE OXIDE CATALYST |
JP4813758B2 (ja) | 2003-02-27 | 2011-11-09 | æ ªåŒäŒç€Ÿæ¥æ¬è§Šåª | è€åé žåç©è§Šåªããã³ãããçšããã¢ã¯ãªã«é žã®è£œé æ¹æ³ |
US20040192973A1 (en) * | 2003-03-31 | 2004-09-30 | Saudi Basic Industries Corporation | Mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
JP4185404B2 (ja) * | 2003-05-28 | 2008-11-26 | æ ªåŒäŒç€Ÿæ¥æ¬è§Šåª | äžé£œåã¢ã«ãããããã³äžé£œåã«ã«ãã³é žè£œé çšè§Šåªããã®è£œé æ¹æ³ãããã³äžé£œåã¢ã«ãããããã³äžé£œåã«ã«ãã³é žã®è£œé æ¹æ³ |
EP2295136A4 (en) | 2008-06-30 | 2011-12-28 | Nippon Catalytic Chem Ind | METHOD OF PACKAGING A SOLID PARTICLE SUBSTANCE IN A MULTI-TUBE FIXED BED REACTOR |
JP2011121048A (ja) | 2009-12-09 | 2011-06-23 | Rohm & Haas Co | åºäœè§Šåªç©è³ªããã¬ã³ããã管ç¶æ§é ç©ã«è£ å¡«ããæ¹æ³ |
-
1982
- 1982-10-22 JP JP57184668A patent/JPS5976541A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5976541A (ja) | 1984-05-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4537874A (en) | Catalyst for production of unsaturated aldehydes | |
JP3786297B2 (ja) | 觊åªã®è£œé æ¹æ³ | |
JPH04118051A (ja) | éã»ã¢ã³ãã¢ã³ã»ã¢ãªããã³å«æé žåç©è§Šåªçµæç©ããã³ãã®è£œæ³ | |
WO1995005241A1 (en) | Ammoxidation catalyst composition | |
KR101331766B1 (ko) | ë¶í¬í ìë°íìŽë ë° ë¶í¬í 칎복ì€ì°ì ì ì¡°ì ì¬ì©íêž° ìí ìŽë§€ì ì ì¡°ë°©ë² ë° ë¶í¬í ìë°íìŽë ë° ë¶í¬í 칎복ì€ì°ì ì ì¡°ë°©ë² | |
JPH0210695B2 (ja) | ||
JPH0441454A (ja) | ã¡ã¿ã¯ãã¬ã€ã³ã®è£œé æ¹æ³ | |
JP3465350B2 (ja) | ã¡ã¿ã¯ãªã«é žè£œé çšè§Šåªã®è£œé æ³ | |
JPH0232017B2 (ja) | ||
JP3939187B2 (ja) | äžé£œåã¢ã«ãããã®è£œé æ¹æ³ | |
JPH0547265B2 (ja) | ||
JP2002356450A (ja) | ã¡ã¿ã¯ãã¬ã€ã³ããã³ã¡ã¿ã¯ãªã«é žã®è£œé æ¹æ³ | |
JPS63145249A (ja) | ã¡ã¿ã¯ãªã«é žããã³ïŒãŸãã¯ã¡ã¿ã¯ãã¬ã€ã³ã®è£œæ³ | |
JPH0212619B2 (ja) | ||
JPS6033539B2 (ja) | é žåçšè§Šåªããã³ãã®èª¿è£œæ³ | |
JPH09313943A (ja) | è€åé žåç©è§Šåªåã³ã¡ã¿ã¯ãªã«é žã®è£œé æ¹æ³ | |
JPH0763625B2 (ja) | é žåçšã¢ãªããã³é žé觊åªã®è£œé æ¹æ³ | |
JP2520279B2 (ja) | ã¢ã¯ãªããããªã«ã®è£œé æ¹æ³ | |
JP2003164763A (ja) | ãããã¬ã³é žåçšè€åé žåç©è§Šåªã®è£œé æ¹æ³ | |
JP4273565B2 (ja) | äžé£œåã¢ã«ãããåã³äžé£œåã«ã«ãã³é žåæçšã®è€åé žåç©è§Šåªã®è£œé æ³ | |
JPS6322536A (ja) | ãã«ã ã¢ã«ãããã®è£œé æ¹æ³ | |
JP2004130261A (ja) | äžé£œåã¢ã«ãããããã³äžé£œåã«ã«ãã³é žã®åæçšè§Šåªã®è£œé æ¹æ³ | |
JP2003205240A (ja) | è€åé žåç©è§Šåªã®è£œé æ¹æ³ | |
JP3313968B2 (ja) | äžé£œåã¢ã«ãããåã³äžé£œåã«ã«ãã³é žåæçšè§Šåªã®è£œé æ³ | |
JPS615043A (ja) | ã¡ã¿ã¯ãªã«é žè£œé çšè§Šåªã®èª¿è£œæ¹æ³ |