JP5479286B2 - Catalyst for producing ethylene oxide and method for producing ethylene oxide - Google Patents
Catalyst for producing ethylene oxide and method for producing ethylene oxide Download PDFInfo
- Publication number
- JP5479286B2 JP5479286B2 JP2010219386A JP2010219386A JP5479286B2 JP 5479286 B2 JP5479286 B2 JP 5479286B2 JP 2010219386 A JP2010219386 A JP 2010219386A JP 2010219386 A JP2010219386 A JP 2010219386A JP 5479286 B2 JP5479286 B2 JP 5479286B2
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- Prior art keywords
- catalyst
- ethylene oxide
- cesium
- water
- carrier
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 149
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000011734 sodium Substances 0.000 claims description 72
- 229910052792 caesium Inorganic materials 0.000 claims description 61
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 56
- 229910052708 sodium Inorganic materials 0.000 claims description 48
- 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 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052702 rhenium Inorganic materials 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 17
- 239000010937 tungsten Substances 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 8
- 238000005277 cation exchange chromatography Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 18
- 239000012018 catalyst precursor Substances 0.000 description 17
- 239000011148 porous material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- -1 oxides thereof Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XZQYTGKSBZGQMO-UHFFFAOYSA-I Rhenium(V) chloride Inorganic materials Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003426 co-catalyst 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
- 239000000571 coke Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000008120 corn starch 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 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
- 229910017604 nitric acid 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
- 235000014571 nuts Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- RQZVTOHLJOBKCW-UHFFFAOYSA-M silver;7,7-dimethyloctanoate Chemical compound [Ag+].CC(C)(C)CCCCCC([O-])=O RQZVTOHLJOBKCW-UHFFFAOYSA-M 0.000 description 1
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 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)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Description
本発明は、エチレンを気相酸化することでエチレンオキシドを製造するための触媒および当該触媒を用いたエチレンオキシドの製造方法である。 The present invention is a catalyst for producing ethylene oxide by vapor phase oxidation of ethylene and a method for producing ethylene oxide using the catalyst.
エチレンを銀触媒の存在下で分子状酸素含有ガスにより接触気相酸化してエチレンオキシドを製造することは工業的に広く行われている。この接触気相酸化に用いる銀触媒については、その担体、担持方法、反応促進剤の種類やその添加量などに関し、多くの技術が提案されている。 It is widely used industrially to produce ethylene oxide by catalytic vapor phase oxidation of ethylene with a molecular oxygen-containing gas in the presence of a silver catalyst. With regard to the silver catalyst used for this catalytic gas phase oxidation, many techniques have been proposed with respect to the carrier, the loading method, the type of reaction accelerator, the amount added, and the like.
銀を主成分に用い他成分として、レニウム／その化合物及びアルカリ金属等の他の金属／その化合物を用いるものが多く提案されている（引用文献１他）。当該触媒成分は担体に担持され触媒を形成するものであり、当該触媒成分および担体において以下の技術が提案されている。例えば、担体ならびに担体上に付着させられた銀、レニウム助触媒、第１の共助触媒および第２の共助触媒からなる触媒が開示されており、そこでの第１の共助触媒はイオウ、リン、ホウ素およびこれらの混合物から選択され、第２の共助触媒はタングステン、モリブデン、クロムおよびこれらの混合物から選択される（引用文献１）。また、銀（Ａｇ）、セシウム（Ｃｓ）、レニウム（Ｒｅ）及び担体から成り、担体に必要に応じ前処理としてアルカリ金属を担持させ、次いで、ＡｇとＣｓとＲｅを担持させて得られる触媒であって、上記担体の比表面積や担体のＳｉＯ２及びＮａ２Oの含有量の重量比、上記担体比表面積当たりのレニウム含有率、さらにＣｓ／Ｒｅモル比等について種々規定した酸化エチレン製造用触媒が開示されている（引用文献２）。これらは担体と触媒成分との関係や触媒調製方法および触媒の反応条件により、性能が左右され十分満足できるとはいいがたいものである。 Many proposals have been made using silver as a main component and using other metals / compounds such as rhenium / compounds and alkali metals as other components (Cited Document 1 and others). The catalyst component is supported on a carrier to form a catalyst, and the following techniques have been proposed for the catalyst component and the carrier. For example, a catalyst comprising a support and silver, rhenium cocatalyst deposited on the support, a first co-promoter and a second co-promoter is disclosed, wherein the first co-promoter is sulfur, phosphorus, boron And the second co-promoter is selected from tungsten, molybdenum, chromium and mixtures thereof (Cited document 1). Further, it is a catalyst comprising silver (Ag), cesium (Cs), rhenium (Re) and a carrier, and an alkali metal supported on the carrier as a pretreatment if necessary, and then supporting Ag, Cs and Re. A catalyst for ethylene oxide production in which the specific surface area of the support, the weight ratio of the SiO 2 and Na 2 O contents of the support, the rhenium content per specific surface area of the support, and the Cs / Re molar ratio are variously defined. Is disclosed (Cited document 2). These performances depend on the relationship between the support and the catalyst components, the catalyst preparation method, and the reaction conditions of the catalyst, and are not satisfactory.
特許文献１では、第1のレニウム共助触媒は、イオウ、リン、ホウ素、およびこれらの混合物から選択され得るが、特にイオウやリンは、触媒の反応熱により触媒表面より揮散し易く、触媒組成によっては、選択率及び活性の急激な低下を引き起こすという問題がある。また、特許文献２では、触媒反応の進行と共に、アルカリ金属で前処理した担体から当該アルカリ金属の一部が触媒主成分の銀上に移動し、銀と助触媒の間の相互作用を変化させ、触媒組成によっては、選択率及び活性の急激な低下を引き起こすという問題がある。これらの技術では、各種の触媒や担体の組成および物性が提案されているが、単に組成および物性等のみに着目するに止まっている。本発明は、単に触媒全体の組成ではなく、反応ガス条件に適合し、触媒反応に実質的に関与しうる触媒表面成分の有効量を提案し、触媒の選択性および触媒寿命（耐久性）に優れるエチレンオキシド製造用触媒を提供することを目的とする。また、本発明は、上記触媒を用いてエチレンオキシドを製造する方法を提供することをも目的とする。 In Patent Document 1, the first rhenium co-promoter can be selected from sulfur, phosphorus, boron, and a mixture thereof. In particular, sulfur and phosphorus are easily evaporated from the catalyst surface by the reaction heat of the catalyst, and depending on the catalyst composition. Has the problem of causing a sharp drop in selectivity and activity. Further, in Patent Document 2, as the catalytic reaction proceeds, a part of the alkali metal moves from the carrier pretreated with the alkali metal onto the silver of the catalyst main component, thereby changing the interaction between the silver and the promoter. Depending on the catalyst composition, there is a problem that the selectivity and the activity are rapidly decreased. In these techniques, the composition and physical properties of various catalysts and carriers have been proposed, but only attention is paid to the composition and physical properties. The present invention proposes an effective amount of catalyst surface components that can be adapted to the reaction gas conditions and can substantially participate in the catalytic reaction, not just the composition of the entire catalyst, and to improve catalyst selectivity and catalyst life (durability). An object is to provide an excellent catalyst for producing ethylene oxide. Another object of the present invention is to provide a method for producing ethylene oxide using the above catalyst.
本発明者らは、上記課題を解決すべく鋭意研究した結果、触媒活性成分として銀、助触媒成分としてセシウム、および担体としてナトリウムを含むα−アルミナからなる酸化エチレン製造用触媒において、触媒表面に存在する微量の水溶出性ナトリウムが特定の範囲にあるとき、セシウムの選択率向上効果をさらに増大さる。特に助触媒成分としてセシウムに加え、レニウム、タングステンを含む当該酸化エチレン製造用触媒において、セシウム、レニウム、タングステンの選択率向上効果をさらに増大させエチレンオキシドを高効率、高選択率で製造可能なエチレンオキシド製造用触媒が提供されうることを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors have found that in the catalyst for ethylene oxide production comprising α-alumina containing silver as a catalytic active component, cesium as a promoter component, and sodium as a support, When the trace amount of water-eluting sodium present is in a specific range, the effect of improving the selectivity of cesium is further increased. In particular, in the ethylene oxide production catalyst containing rhenium and tungsten in addition to cesium as a co-catalyst component, ethylene oxide production that can further enhance the selectivity improvement effect of cesium, rhenium and tungsten and produce ethylene oxide with high efficiency and high selectivity The present inventors have found that a catalyst for use can be provided.
即ち、本発明は、銀を触媒活性成分とし、セシウムを助触媒成分としナトリウムを含むα−アルミナ担体に当該触媒活性成分および当該助触媒を担持した触媒であって、水溶出性ナトリウムが１．０〜１１．５μｍｏｌ（触媒１ｇ当たり）であることを特徴とするエチレンオキシド製造用触媒である。ここで水溶出性ナトリウムは、下記条件により測定されるものである。
（１）触媒３．０ｇを１００ｍｌの純水に投入し１００℃で３０分間煮沸した後、液１を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸した後、液２を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸し、液３を除く。
（２）液１〜３を集めて、２００ｍｌに調整する。
（３）当該調整した液を陽イオンクロマトグラフィーにより、水溶出性ナトリウムの濃度を測定する。
That is, the present invention is a catalyst in which silver is a catalytically active component, cesium is a cocatalyst component, and the α-alumina carrier containing sodium is loaded with the catalytically active component and the cocatalyst. It is a catalyst for ethylene oxide production characterized by 0 to 11.5 μmol (per gram of catalyst). Here, water-eluting sodium is measured under the following conditions.
(1) After adding 3.0 g of catalyst to 100 ml of pure water and boiling at 100 ° C. for 30 minutes, liquid 1 was removed, 100 ml of pure water was added again and boiling at 100 ° C. for 30 minutes, and then liquid 2 was added. In addition, 100 ml of pure water is newly added and boiled at 100 ° C. for 30 minutes to remove liquid 3.
(2) Collect liquids 1-3 and adjust to 200 ml.
(3) The concentration of water-eluting sodium is measured by cation chromatography on the adjusted liquid.
本発明のエチレンオキシド製造用触媒は選択性および触媒寿命（耐久性）に優れる。このため、本発明の触媒を使用することによって、エチレンオキシドを長期に亘って高選択率で製造できる。エチレンオキシドの生産規模は、年間約１８００万トンと見積もられており、非常に大きい。このため、例えば、１００日後の選択率の低下が僅か１％抑えられるだけでも、原料エチレンの使用量が著しく節約され、その経済的効果は非常に大きい。このような事情から、より優れた選択性を有する銀触媒の開発が当該技術分野の研究者の継続的なテーマとなっている。 The ethylene oxide production catalyst of the present invention is excellent in selectivity and catalyst life (durability). For this reason, by using the catalyst of the present invention, ethylene oxide can be produced with high selectivity over a long period of time. The production scale of ethylene oxide is estimated to be about 18 million tons per year and is very large. For this reason, for example, even if the decrease in selectivity after 100 days is suppressed by only 1%, the amount of raw ethylene used is significantly saved, and its economic effect is very large. Under such circumstances, the development of silver catalysts having better selectivity has been a continuous theme for researchers in the technical field.
以下に本発明を具体的に説明するが、本発明の効果を奏する限り下記記載に限定されるものではない。 The present invention will be specifically described below, but is not limited to the following description as long as the effects of the present invention are exhibited.
本発明は、銀を触媒活性成分とし、セシウムを助触媒成分とし、ナトリウムを含むα−アルミナ担体に当該触媒活性成分および当該助触媒成分を担持した触媒であって、水溶出性ナトリウムが１．０〜１１．５μｍｏｌ（触媒１ｇ当たり）であることを特徴とするエチレンオキシド製造用触媒を提供する。ここで水溶出性ナトリウムは下記条件により測定されるものである。
（１）触媒３．０ｇを１００ｍｌの純水に投入し１００℃で３０分間煮沸した後、液１を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸した後、液２を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸し、液３を除く。
（２）液１〜３を集めて、２００ｍｌに調整する。
（３）当該調整した液を陽イオンクロマトグラフィーにより、ナトリウムの濃度を測定する。
The present invention is a catalyst in which silver is used as a catalytic active component, cesium is used as a promoter component, and the catalytic active component and the promoter component are supported on an α-alumina carrier containing sodium. Provided is a catalyst for producing ethylene oxide, which is 0 to 11.5 μmol (per gram of catalyst). Here, water-eluting sodium is measured under the following conditions.
(1) After adding 3.0 g of catalyst to 100 ml of pure water and boiling at 100 ° C. for 30 minutes, liquid 1 was removed, 100 ml of pure water was added again and boiling at 100 ° C. for 30 minutes, and then liquid 2 was added. In addition, 100 ml of pure water is newly added and boiled at 100 ° C. for 30 minutes to remove liquid 3.
(2) Collect liquids 1-3 and adjust to 200 ml.
(3) The sodium concentration is measured by cation chromatography of the adjusted liquid.
本発明で定めた水溶出性ナトリウム量は、一般的な陽イオンクロマトグラフ装置によって定量することができる。 The amount of water-eluting sodium determined in the present invention can be quantified by a general cation chromatograph.
本発明による触媒に含まれる水溶出性ナトリウム量は１．０〜１１．５μｍｏｌ（触媒１ｇ当たり）であり、このような量で水溶出性ナトリウムを含むことにより、セシウムの添加効果である選択性向上効果を増大させることができる。また、更なる助触媒成分としてレニウム、タングステンを添加することができるが、これらが有する選択性を向上効果も増加させることができる。
好ましい水溶出性ナトリウム量は２．０〜１０．０μｍｏｌ（触媒１ｇ当たり）であり、より好ましい水溶出性ナトリウム量は２．５〜９．５μｍｏｌ（触媒１ｇ当たり）である。なお、当該水溶出性ナトリウム量が１．０μｍｏｌ（触媒１ｇ当たり）より少ない場合は、セシウム、特にセシウム、レニウム、タングステンによる選択率向上効果が得られず、１１．５μｍｏｌ（触媒１ｇ当たり）より多い場合は触媒表面のナトリウムが過剰となり活性および選択率ともに低下する。
The amount of water-eluting sodium contained in the catalyst according to the present invention is 1.0 to 11.5 μmol (per gram of catalyst). By including water-eluting sodium in such an amount, selectivity which is an effect of adding cesium The improvement effect can be increased. Moreover, although rhenium and tungsten can be added as a further promoter component, the selectivity which these have can also be increased.
A preferable water-eluting sodium amount is 2.0 to 10.0 μmol (per 1 g of catalyst), and a more preferable water-eluting sodium amount is 2.5 to 9.5 μmol (per 1 g of catalyst). When the amount of water-eluting sodium is less than 1.0 μmol (per gram of catalyst), the effect of improving selectivity by cesium, particularly cesium, rhenium, and tungsten cannot be obtained, and the amount is more than 11.5 μmol (per gram of catalyst). In this case, sodium on the catalyst surface becomes excessive, and both the activity and selectivity are lowered.
また、本発明による触媒において、上記（１）および（２）の条件により２００ｍｌに調整された水溶液は水溶出性セシウムも含む。当該水溶出性セシウム量は４．５〜７．４μｍｏｌ（触媒１ｇ当たり）であり、当該触媒はこのような量で水溶出性セシウムを含むことにより、高い選択率が得られる利点がある。好ましい水溶出性セシウム量は４．５〜７．０μｍｏｌ（触媒１ｇ当たり）であり、より好ましい水溶出性セシウム量は４．５〜６．５μｍｏｌ（触媒１ｇ当たり）である。なお、当該水溶出性セシウムが４．５μｍｏｌ（触媒１ｇ当たり）より少ない場合は高い選択率が得られず、７．４μｍｏｌ（触媒１ｇ当たり）より多い場合は、触媒表面のセシウムが過剰となり活性および選択率ともに低下する。 In the catalyst according to the present invention, the aqueous solution adjusted to 200 ml according to the above conditions (1) and (2) also contains water-eluting cesium. The amount of water-eluting cesium is 4.5 to 7.4 μmol (per gram of catalyst), and the catalyst contains water-eluting cesium in such an amount, so that there is an advantage that high selectivity can be obtained. A preferable amount of water-eluting cesium is 4.5 to 7.0 μmol (per gram of catalyst), and a more preferable amount of water-eluting cesium is 4.5 to 6.5 μmol (per gram of catalyst). When the water-eluting cesium is less than 4.5 μmol (per gram of catalyst), high selectivity cannot be obtained. When the water-eluting cesium is higher than 7.4 μmol (per gram of catalyst), the cesium on the catalyst surface becomes excessive and active and The selectivity decreases.
当該水溶出性ナトリウムは担体由来であり、当該水溶出性セシウムは助触媒成分由来であるが、これらの値のモル比（Ｃｓ／Ｎａモル比）は担体の比表面積（窒素ガスを用いたＢＥＴ法による測定、以下、ＢＥＴ比表面積と略して記載する。）にも依存性が見られる。即ち、当該水溶出性ナトリウムに対する当該水溶出性セシウムのモル比（Ｃｓ／Ｎａモル比）を担体のＢＥＴ比表面積で除した値（以下、（Ｃｓ／Ｎａモル比）／担体比表面積と記載することもある。）は０．７〜５．３ｇ／ｍ２であると、ナトリウムがセシウム、特にセシウム、レニウム、タングステンの選択率向上効果を促進するため、高い選択率が得られる利点がある。好ましい（Ｃｓ／Ｎａモル比）／担体比表面積は０．７〜５．０ｇ／ｍ２であり、より好ましい（Ｃｓ／Ｎａモル比）／担体比表面積は０．７〜４．５ｇ／ｍ２である。なお、（Ｃｓ／Ｎａモル比）／担体比表面積が０．７ｇ／ｍ２より少ない場合、セシウムに対して過剰のナトリウムがセシウム、特にセシウム、レニウム、タングステンの選択率向上効果を阻害するため高い選択率が得られず、また当該過剰のナトリウムが活性点を被覆するため活性も低い。一方、（Ｃｓ／Ｎａモル比）／担体比表面積が５．３ｇ／ｍ２より多い場合は、セシウムに対してナトリウムが不足するためセシウム、特にセシウム、レニウム、タングステンの選択率向上効果が十分に得られず高い選択率が得られない。 The water-eluting sodium is derived from the carrier, and the water-eluting cesium is derived from the promoter component. The molar ratio of these values (Cs / Na molar ratio) is the specific surface area of the carrier (BET using nitrogen gas). Dependency is also observed in the measurement by the method, hereinafter abbreviated as BET specific surface area. That is, a value obtained by dividing the molar ratio of the water-eluting cesium to the water-eluting sodium (Cs / Na molar ratio) by the BET specific surface area of the carrier (hereinafter referred to as (Cs / Na molar ratio) / carrier specific surface area). In the case of 0.7 to 5.3 g / m 2 , sodium promotes the effect of improving the selectivity of cesium, particularly cesium, rhenium, and tungsten, so that there is an advantage that a high selectivity can be obtained. Preferred (Cs / Na molar ratio) / support specific surface area is 0.7 to 5.0 g / m 2 , more preferred (Cs / Na molar ratio) / support specific surface area is 0.7 to 4.5 g / m 2. It is. In addition, when (Cs / Na molar ratio) / support specific surface area is less than 0.7 g / m 2 , the excess sodium with respect to cesium is high because it inhibits the selectivity improvement effect of cesium, particularly cesium, rhenium, and tungsten. Selectivity cannot be obtained, and the activity is low because the excess sodium covers the active site. On the other hand, when the (Cs / Na molar ratio) / support specific surface area is more than 5.3 g / m 2 , sodium is insufficient with respect to cesium, so that the effect of improving the selectivity of cesium, particularly cesium, rhenium and tungsten is sufficient. A high selectivity cannot be obtained.
（担体）
本発明において、担体組成は、α−アルミナを主成分とするものであればよく、担体が「α−アルミナを主成分とする」とは、担体におけるα−アルミナの含有量は担体の全質量１００質量％に対して、７０質量％以上含まれることを意味する。好ましくは９０質量％以上であり、より好ましくは９５質量％以上含まれるものである。
(Carrier)
In the present invention, the carrier composition only needs to have α-alumina as a main component, and the carrier “having α-alumina as the main component” means that the content of α-alumina in the carrier is the total mass of the carrier. It means that 70 mass% or more is contained with respect to 100 mass%. Preferably it is 90 mass% or more, More preferably, 95 mass% or more is contained.
他に含まれる成分としてケイ素、ナトリウム等があり、例えば担体にケイ素（Ｓｉ）をＳｉＯ２換算で０．１〜５．０質量％、ナトリウム（Ｎａ）をＮａ２Ｏ換算で０．００１〜１．０質量％含むものであっても良い。以下、「％」で表示するが特に記載しないかぎりは担体全体で１００質量％とする。 Other components include silicon, sodium, and the like. For example, silicon (Si) is 0.1 to 5.0% by mass in terms of SiO 2 and sodium (Na) is 0.001 to 1 in terms of Na 2 O on the carrier. It may contain 0.0 mass%. Hereinafter, it is expressed in “%”, but unless otherwise specified, the whole carrier is 100% by mass.
上記成分以外に他の成分としては、例えば、アルカリ金属（Ｎａを除く）及びアルカリ土類金属ならびにこれらの酸化物、遷移金属およびこれらの酸化物などが挙げられる。このうち、ナトリウム及びセシウム以外のアルカリ金属を実質的に含まないことが好ましく、より好ましくはナトリウム及びセシウム以外のアルカリ金属の含有量（酸化物換算）は、担体の全質量１００質量％に対して、０〜０．１質量％含まれるものである。また、アルカリ土類金属の好ましい含有量（酸化物換算）は、担体の全質量１００質量％に対して、０〜０．１質量％含まれるものである。また、遷移金属の好ましい含有量（酸化物換算）は、担体の全質量１００質量％に対して、０〜０．３質量％含まれるものである。 In addition to the above components, examples of other components include alkali metals (excluding Na) and alkaline earth metals, oxides thereof, transition metals and oxides thereof. Among these, it is preferable that alkali metals other than sodium and cesium are substantially not included, and more preferably, the content of alkali metals other than sodium and cesium (as oxide) is based on 100% by mass of the total mass of the carrier. 0 to 0.1% by mass. Moreover, preferable content (in oxide conversion) of alkaline-earth metal is 0-0.1 mass% with respect to 100 mass% of the total mass of a support | carrier. Moreover, preferable content (in oxide conversion) of a transition metal is 0-0.3 mass% contained with respect to 100 mass% of the total mass of a support | carrier.
上記担体原料であるα−アルミナは通常粉体であり、その純度は９０％以上、好ましくは９５％以上、更に好ましくは９９％以上、特に好ましくは９９．５％以上のものが用いられる。α−アルミナ粉体のほかに、酸化アルミナ、特に無定形のアルミナ、シリカ、シリカアルミ、ムライトなど（これらを「無定形アルミナ等」と総称する）；酸化セシウムを除く、酸化カリウム、酸化ナトリウムなどのアルカリ金属酸化物およびアルカリ土類金属酸化物など（これらを「アルカリ等」と総称する）；酸化鉄、酸化チタンなどの遷移金属酸化物を含んでいてもよい。なお、担体を成型体にする前の原料α−アルミナ粉体には、微量ながらナトリウム（酸化ナトリウム）が含まれていることがある。この場合には、予めその粉体中のナトリウム量を把握することにより、担体が特定量のナトリウム含有量となるように、担体調製時にナトリウム化合物を添加し、担体を得ることができる。 The carrier raw material α-alumina is usually a powder having a purity of 90% or higher, preferably 95% or higher, more preferably 99% or higher, particularly preferably 99.5% or higher. In addition to α-alumina powder, alumina oxide, especially amorphous alumina, silica, silica aluminum, mullite, etc. (these are collectively referred to as “amorphous alumina etc.”); excluding cesium oxide, potassium oxide, sodium oxide, etc. Alkali metal oxides and alkaline earth metal oxides (collectively referred to as “alkalis etc.”); transition metal oxides such as iron oxide and titanium oxide may be included. The raw material α-alumina powder before forming the carrier into a molded body may contain a small amount of sodium (sodium oxide). In this case, by previously grasping the amount of sodium in the powder, the carrier can be obtained by adding a sodium compound at the time of preparing the carrier so that the carrier has a specific amount of sodium content.
担体原料のα−アルミナ粉体の粒径に関しても特に制限はないが、α−アルミナ粉体の一次粒子径は、好ましくは０．０１〜１００μｍであり、より好ましくは０．１〜２０μｍであり、さらに好ましくは０．５〜１０μｍであり、特に好ましくは１〜５μｍである。また当該α−アルミナ粉体の二次粒子径は、好ましくは０．１〜１，０００μｍであり、より好ましくは１〜５００μｍであり、さらに好ましくは１０〜２００μｍであり、特に好ましくは３０〜１００μｍである。 The particle diameter of the carrier raw material α-alumina powder is not particularly limited, but the primary particle diameter of the α-alumina powder is preferably 0.01 to 100 μm, more preferably 0.1 to 20 μm. More preferably, it is 0.5-10 micrometers, Most preferably, it is 1-5 micrometers. The secondary particle diameter of the α-alumina powder is preferably 0.1 to 1,000 μm, more preferably 1 to 500 μm, still more preferably 10 to 200 μm, and particularly preferably 30 to 100 μm. It is.
担体原料に用いるα−アルミナ粉体の比表面積（窒素ガスを用いたＢＥＴ法による測定、以下、ＢＥＴ比表面積と略す。）に関しても特に制限はないが、α−アルミナ粉体のＢＥＴ比表面積は、好ましくは０．０１〜２０ｍ２／ｇであり、より好ましくは０．１〜１０ｍ２／ｇであり、さらに好ましくは０．１〜５ｍ２／ｇであり、特に好ましくは０．３〜４ｍ２／ｇである。 There is no particular limitation on the specific surface area of the α-alumina powder used for the carrier material (measured by the BET method using nitrogen gas, hereinafter abbreviated as BET specific surface area), but the BET specific surface area of the α-alumina powder is Preferably, it is 0.01-20 m < 2 > / g, More preferably, it is 0.1-10 m < 2 > / g, More preferably, it is 0.1-5 m < 2 > / g, Most preferably, it is 0.3-4 m. 2 / g.
また、当該α−アルミナ粉体の線収縮率は１２〜２０％のものが好適に用いられる。ここで示す「線収縮率」とは、α−アルミナ粉体に約１〜５質量％のフラックスを添加し、約５０ＭＰａの圧力で成形した後、約１６００〜１７００℃で２〜３時間焼成したときの長さ方向の収縮率を指す。 Moreover, the linear shrinkage rate of the α-alumina powder is preferably 12 to 20%. “Linear shrinkage” shown here is about 1-5 mass% flux added to α-alumina powder, molded at a pressure of about 50 MPa, and then fired at about 1600-1700 ° C. for 2-3 hours. It refers to the contraction rate in the length direction.
また、担体はケイ素（Ｓｉ）を、ＳｉＯ２換算で０．１〜５．０質量％含むこともできる。このような量でケイ素を含むことにより、セシウム、特にセシウム、レニウムおよびタングステンの触媒機能低下を抑制・防止でき、高選択率を長期間安定的に維持できるという利点がある。好ましくは、担体中のＳｉ含有量（ＳｉＯ２換算）は、担体の全質量１００質量％に対して、０．１〜３．０質量％、さらに好ましくは０．５〜２．５質量％である。なお、担体中のＳｉ含有量（ＳｉＯ２換算）が上記下限を下回る場合には、十分な寿命安定性が得られないおそれがあり、逆に上限を超える場合には、初期から高い選択率が得られないおそれがある。 Further, the support of silicon (Si), but may also include 0.1 to 5.0 wt% in terms of SiO 2. By including silicon in such an amount, it is possible to suppress / prevent deterioration of the catalytic function of cesium, particularly cesium, rhenium and tungsten, and there is an advantage that high selectivity can be stably maintained for a long time. Preferably, the Si content (in terms of SiO 2 ) in the carrier is 0.1 to 3.0% by mass, more preferably 0.5 to 2.5% by mass with respect to 100% by mass of the total mass of the carrier. is there. When the Si content in the carrier (in terms of SiO 2 ) is below the lower limit, sufficient life stability may not be obtained. Conversely, when the upper limit is exceeded, high selectivity is obtained from the beginning. May not be obtained.
また、当該ケイ素原料としては、酸化ケイ素、シリカゾル、窒化ケイ素、炭化ケイ素、シラン、硫化ケイ素などの共有結合化合物；ケイ酸ナトリウム、ケイ酸アンモニウム、アルミノケイ酸ナトリウム、アルミノケイ酸アンモニウム、リンケイ酸ナトリウム、リンケイ酸アンモニウムなどのケイ酸塩類；長石、粘土などのケイ素を含むシリカの複塩；およびシリカ混合物を挙げることができる。このなかでも、酸化ケイ素、ケイ酸ナトリウム、粘土などのケイ素を含むシリカの複塩などを使用することが好ましい。ここで、ケイ素化合物の添加量は、上記したようなＳｉ含有量（ＳｉＯ２換算）となるような量に調節される。 In addition, the silicon raw material includes covalently bonded compounds such as silicon oxide, silica sol, silicon nitride, silicon carbide, silane, and silicon sulfide; sodium silicate, ammonium silicate, sodium aluminosilicate, ammonium aluminosilicate, sodium phosphosilicate, and phosphorus silicate. Mention may be made of silicates such as ammonium acid; double salts of silica containing silicon such as feldspar and clay; and silica mixtures. Among these, it is preferable to use a double salt of silica containing silicon such as silicon oxide, sodium silicate, or clay. Here, the addition amount of the silicon compound is adjusted to such an amount that the Si content (in terms of SiO 2 ) as described above is obtained.
担体に含まれるナトリウム（Ｎａ）は、Ｎａ２Ｏ換算で０．００１〜１．０質量％含まれていてもよく、このような量でナトリウムを含むことにより、触媒性能の低下を抑制・防止できる利点がある。好ましくは、担体中のＮａ含有量（Ｎａ２Ｏ換算）は、担体の全質量１００質量％に対して、０．００１〜０．９質量％、より好ましくは０．００１質量％以上０．８質量％未満、さらにより好ましくは０．００１〜０．７５質量％、特に好ましくは０．００５〜０．７質量％である。なお、担体中のＮａ含有量（Ｎａ２Ｏ換算）が上記下限を下回る場合には、十分な寿命安定性が得られないおそれがあり、逆に上記上限を超える場合には、初期から高い選択率が得られないおそれがある。 Sodium (Na) contained in the carrier may be contained in an amount of 0.001 to 1.0% by mass in terms of Na 2 O, and by containing sodium in such an amount, deterioration in catalyst performance is suppressed / prevented. There are advantages you can do. Preferably, the Na content (Na 2 O equivalent) in the carrier is 0.001 to 0.9% by mass, more preferably 0.001% by mass or more and 0.8% with respect to 100% by mass of the total mass of the carrier. It is less than mass%, still more preferably 0.001 to 0.75 mass%, particularly preferably 0.005 to 0.7 mass%. If the Na content (Na 2 O equivalent) in the support is below the lower limit, sufficient life stability may not be obtained. Conversely, if the content exceeds the upper limit, the initial selection is high. The rate may not be obtained.
ナトリウム原料としては、硝酸ナトリウム、炭酸ナトリウム、水酸化ナトリウムなどの無機塩、および酢酸ナトリウム、ギ酸ナトリウム、クエン酸ナトリウムなどの有機酸、およびカルボキシメチルセルロースナトリウムなどの高分子カルボン酸塩を用いることができる。 As the sodium raw material, inorganic salts such as sodium nitrate, sodium carbonate, and sodium hydroxide, organic acids such as sodium acetate, sodium formate, and sodium citrate, and polymer carboxylates such as sodium carboxymethyl cellulose can be used. .
なお、上述した担体の組成や各成分の含有量は、蛍光Ｘ線分析法を用いて決定できる。より具体的には、測定装置としてＲＩＧＡＫＵ製ＲＩＸ２０００を用い、ファンダメンタルパラメータ法（ＦＰ法）或いは検量線法にて測定することができる。 The composition of the carrier and the content of each component described above can be determined using a fluorescent X-ray analysis method. More specifically, RIX2000 manufactured by RIGAKU can be used as a measuring apparatus, and measurement can be performed by a fundamental parameter method (FP method) or a calibration curve method.
担体は上記成分を混合し一定の形状に成形し製造するものであるが、成形する際にバインダーを添加して製造することもできる。例えば、当該バインダーは、滑性を付与することによって押出工程を容易にせしめる。無機バインダーには、特に硝酸または酢酸のようなペプタイザーと組合せたアルミナゲルが含まれる。有機バインダーとしては、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、コーンスターチまたはそれらのアルカリ金属塩などを挙げることができる。この中でも、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウムなどを使用することが好ましい。 The carrier is produced by mixing the above components and forming into a certain shape, but it can also be produced by adding a binder at the time of forming. For example, the binder facilitates the extrusion process by imparting lubricity. Inorganic binders include alumina gels combined with a peptizer such as nitric acid or acetic acid. Examples of the organic binder include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, corn starch, or alkali metal salts thereof. Among these, it is preferable to use carboxymethylcellulose, sodium carboxymethylcellulose, and the like.
当該担体を製造する際に気孔形成剤を添加することも好ましい。当該気孔形成剤は、焼成時に担体から完全に除去されて、該担体中に制御された気孔が残るように混合物に添加される材料である。これらの材料は、コークス、炭素粉末、グラファイト、（ポリエチレン、ポリスチレン、ポリカーボネート等のような）粉末プラスチック、セルロースおよびセルロース基材料、おが屑、ならびに粉砕堅果穀（カシュー、くるみ等）のような他の植物材料、のような炭質材料である。炭素基材バインダーもまた気孔形成剤として役に立つことができる。 It is also preferable to add a pore-forming agent when producing the carrier. The pore-forming agent is a material that is completely removed from the carrier during firing and added to the mixture so that controlled pores remain in the carrier. These materials include coke, carbon powder, graphite, powdered plastics (such as polyethylene, polystyrene, polycarbonate, etc.), cellulose and cellulose-based materials, sawdust, and other plants such as ground nuts (cashew, walnuts, etc.) Carbonaceous material such as material. Carbon based binders can also serve as pore formers.
（担体の製造方法）
担体は以下のような方法により調製される。少なくともα−アルミナを主成分とするα−アルミナ粉体およびバインダーと、シリカを提供する原料としてのケイ素化合物、他に気孔形成剤と、適当量の水とを加えて十分混練し、押出成形法等により所定の形状、例えば、球状、ペレット状等に成形したのち、必要に応じ乾燥し、ヘリウム、窒素、アルゴン等の不活性ガスおよび／または空気等のガス雰囲気下で１，０００〜１，８００℃、好ましくは１，３００〜１，７００℃で焼成することにより、本発明に係る担体を製造することができる。
(Method for producing carrier)
The carrier is prepared by the following method. An α-alumina powder and binder containing at least α-alumina as a main component, a silicon compound as a raw material for providing silica, a pore forming agent, and an appropriate amount of water are added and kneaded sufficiently, followed by an extrusion molding method. After forming into a predetermined shape such as a spherical shape, a pellet shape, etc., etc., it is dried as necessary, and is 1,000 to 1, under a gas atmosphere such as an inert gas such as helium, nitrogen and argon and / or air. The carrier according to the present invention can be produced by firing at 800 ° C., preferably 1,300 to 1,700 ° C.
担体中のシリカ含有量は、α−アルミナを主成分とする粉体およびケイ素化合物に含まれるシリカ量から算出することができる。担体中のナトリウム含有量は、ケイ素化合物、有機バインダーおよびα−アルミナに含まれるナトリウム量を勘案し調整すればよい。更には、このようにして得られたＳｉＯ２、Ｎａ２Ｏを含有する担体に、ケイ素化合物、ナトリウムを含有する化合物を後添加することで含有量を調整してもよいが、担体調製時にシリカおよびナトリウム化合物を添加することもできる。 The silica content in the carrier can be calculated from the amount of silica contained in the powder mainly composed of α-alumina and the silicon compound. The sodium content in the carrier may be adjusted in consideration of the amount of sodium contained in the silicon compound, organic binder and α-alumina. Furthermore, the content may be adjusted by post-adding a silicon compound or a compound containing sodium to the carrier containing SiO 2 or Na 2 O thus obtained. Sodium compounds can also be added.
担体の比表面積（窒素ガスを用いたＢＥＴ法による測定、以下、ＢＥＴ比表面積と略して記載する。）は、０．５〜３．０ｍ２／ｇである。このような担体を使用することにより、触媒成分を十分量担持しつつ、レニウムおよびタングステン等の触媒成分の移動を抑制・防止でき、性能低下を抑えることができる利点がある。好ましくは、担体のＢＥＴ比表面積は、０．５〜２．５ｍ２／ｇ、より好ましくは０．５〜２．０ｍ２／ｇである。 The specific surface area of the support (measured by the BET method using nitrogen gas, hereinafter abbreviated as BET specific surface area) is 0.5 to 3.0 m 2 / g. By using such a carrier, there is an advantage that the catalyst component such as rhenium and tungsten can be suppressed / prevented from moving while a sufficient amount of the catalyst component is supported, and the performance deterioration can be suppressed. Preferably, the BET specific surface area of the support is 0.5 to 2.5 m 2 / g, more preferably 0.5 to 2.0 m 2 / g.
なお、担体のＢＥＴ比表面積が上記下限を下回ると、吸水率が充分に確保できず、触媒成分の担持が困難になるおそれや触媒成分の分散状態が悪化し性能が低下しやすくなるおそれがある。逆に、担体のＢＥＴ比表面積が上記上限を超える場合には、熱的な劣化などで触媒成分が移動し、反応前と比較して反応中の触媒の担持状態が変化しやすいため、触媒性能の低下度合いが大きくなるおそれがある。 If the BET specific surface area of the support is less than the above lower limit, the water absorption rate cannot be sufficiently secured, and it may be difficult to support the catalyst component, or the dispersed state of the catalyst component may be deteriorated and the performance may be deteriorated. . Conversely, when the BET specific surface area of the support exceeds the above upper limit, the catalyst component moves due to thermal degradation, etc., and the supported state of the catalyst during the reaction is likely to change compared to before the reaction. There is a possibility that the degree of decrease in the increase.
担体の吸水率についても特に制限はないが、好ましくは１０〜７０％であり、より好ましくは２０〜６０％であり、さらに好ましくは３０〜５０％である。担体の吸水率が１０％以上であれば、触媒成分の担持が容易となる。一方、担体の吸水率が７０％以下であれば、担体の強度が実用的な程度に確保されうる。なお、担体の吸水率の値としては、後述する実施例に記載の手法により得られる値を採用するものとする。 Although there is no restriction | limiting in particular also about the water absorption rate of a support | carrier, Preferably it is 10 to 70%, More preferably, it is 20 to 60%, More preferably, it is 30 to 50%. If the water absorption rate of the carrier is 10% or more, the catalyst component can be easily supported. On the other hand, if the water absorption rate of the carrier is 70% or less, the strength of the carrier can be ensured to a practical level. In addition, as a value of the water absorption rate of the carrier, a value obtained by a method described in Examples described later is adopted.
担体の平均細孔径は特に制限されないが、好ましくは０．１〜１０μｍであり、より好ましくは０．２〜４．０μｍであり、さらに好ましくは０．３〜３．０μｍである。担体の平均細孔径が０．１μｍ以上であれば、エチレンオキシド製造時の生成ガスの滞留に伴うエチレンオキシドの逐次酸化が抑制されうる。一方、担体の平均細孔径が１０μｍ以下であれば、担体の強度が実用的な程度に確保されうる。また、担体の細孔容積も特に制限されないが、好ましくは０．１〜１．０ｍＬ／ｇであり、より好ましくは０．２〜０．８ｍＬ／ｇであり、さらに好ましくは０．３〜０．６ｍＬ／ｇである。担体の細孔容積が０．１ｍＬ／ｇ以上であれば、触媒成分の担持が容易となるという点で好ましい。一方、担体の細孔容積が１．０ｍＬ／ｇ以下であれば、担体の強度が実用的な程度に確保されうるという点で好ましい。なお、当該平均細孔径ならびに細孔容積は水銀圧入法により測定したものを指す。水銀圧入法では、２００℃にて少なくとも３０分間脱気した担体をサンプルとし、測定装置としてオートポアＩＩＩ９４２０Ｗ（株式会社島津製作所製）を用い、１．０〜６０，０００ｐｓｉａの圧力範囲及び６０個の測定ポイントで測定される値を採用するものとする。 The average pore diameter of the carrier is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.2 to 4.0 μm, and further preferably 0.3 to 3.0 μm. If the average pore diameter of the support is 0.1 μm or more, the sequential oxidation of ethylene oxide accompanying the retention of the product gas during the production of ethylene oxide can be suppressed. On the other hand, if the average pore diameter of the carrier is 10 μm or less, the strength of the carrier can be ensured to a practical level. The pore volume of the carrier is not particularly limited, but is preferably 0.1 to 1.0 mL / g, more preferably 0.2 to 0.8 mL / g, and still more preferably 0.3 to 0. .6 mL / g. If the pore volume of the carrier is 0.1 mL / g or more, it is preferable in that the catalyst component can be easily supported. On the other hand, if the pore volume of the carrier is 1.0 mL / g or less, it is preferable in that the strength of the carrier can be ensured to a practical level. The average pore diameter and pore volume refer to those measured by mercury porosimetry. In the mercury intrusion method, a carrier deaerated at 200 ° C. for at least 30 minutes is used as a sample, and Autopore III 9420W (manufactured by Shimadzu Corporation) is used as a measuring device, and a pressure range of 1.0 to 60,000 psia and 60 measurements are performed. The value measured at the point shall be adopted.
担体の形状は、特に制限されず、リング状、球状、円柱状、ペレット状のほか、従来公知の知見が適宜参照されうる。また、担体のサイズ（平均直径）についても特に制限はなく、好ましくは３〜２０ｍｍであり、より好ましくは４〜１０ｍｍである。 The shape of the carrier is not particularly limited, and conventionally known knowledge can be appropriately referred to in addition to a ring shape, a spherical shape, a cylindrical shape, and a pellet shape. Moreover, there is no restriction | limiting in particular also about the size (average diameter) of a support | carrier, Preferably it is 3-20 mm, More preferably, it is 4-10 mm.
（触媒成分）
本発明の触媒は、触媒活性成分と助触媒成分とで構成される触媒成分を担体に担持し形成される。詳しくは、上述した担体上に、少なくとも銀（Ａｇ）及びセシウム（Ｃｓ）、特に銀（Ａｇ）、セシウム（Ｃｓ）、レニウム（Ｒｅ）及びタングステン（Ｗ）を含む触媒成分が担持されてなる構成を有するものが好ましい。
(Catalyst component)
The catalyst of the present invention is formed by supporting a catalyst component composed of a catalytically active component and a promoter component on a carrier. Specifically, a structure in which a catalyst component including at least silver (Ag) and cesium (Cs), particularly silver (Ag), cesium (Cs), rhenium (Re), and tungsten (W) is supported on the above-described support. Those having the following are preferred.
上記触媒成分のうち、銀が、主として触媒活性成分としての役割を担う。ここで、銀の含有量（担持量）は、特に制限されず、エチレンオキシドの製造に有効な量で担持すればよい。また、銀の含有量（担持量）は、特に制限されないが、エチレンオキシド製造用触媒の質量基準で（担体及び触媒成分の合計質量基準で；以下、同様）、１〜３０質量％であり、好ましくは５〜２０質量％である。このような範囲であれば、エチレンを分子状酸素含有ガスにより気相酸化してエチレンオキシドを製造する反応を効率よく触媒化できる。 Among the catalyst components, silver mainly plays a role as a catalyst active component. Here, the silver content (supported amount) is not particularly limited, and may be supported in an amount effective for the production of ethylene oxide. The silver content (supported amount) is not particularly limited, but is preferably 1 to 30% by mass based on the mass of the ethylene oxide production catalyst (based on the total mass of the carrier and the catalyst component; the same applies hereinafter). Is 5 to 20% by mass. Within such a range, it is possible to efficiently catalyze the reaction of producing ethylene oxide by vapor phase oxidation of ethylene with a molecular oxygen-containing gas.
また、セシウム（Ｃｓ）は一般に、銀の反応促進剤として作用する。これらの含有量（担持量）は、特に制限されず、エチレンオキシドの製造に有効な量で担持すればよい。また、セシウムの含有量（担持量）は、特に制限されないが、エチレンオキシド製造用触媒の質量基準で、５００〜５０００ｐｐｍであり、好ましくは１０００〜４０００ｐｐｍである。このような範囲であれば、エチレンを分子状酸素含有ガスにより気相酸化してエチレンオキシドを製造する反応を有効に促進できる。
レニウム（Ｒｅ）はセシウムの補助促進剤として作用する。レニウムの含有量（担持量）は、特に制限されないが、エチレンオキシド製造用触媒の質量基準で、５０〜２０００ｐｐｍであり、好ましくは１００〜１０００ｐｐｍである。このような範囲であれば、エチレンを分子状酸素含有ガスにより気相酸化してエチレンオキシドを製造する反応を有効に促進できる。特にレニウムは触媒の選択性の点で重要な要素であると考えられる。このため、上記範囲にレニウム量を制御することによって、触媒の選択性を有効に向上できる。Ｒｅが上記範囲を超えると、選択率の上昇が認められなくなるだけでなく、反応温度を高くする必要があるため、寿命性能に悪影響を及ぼす可能性がある。
Cesium (Cs) generally acts as a silver reaction accelerator. These contents (supported amounts) are not particularly limited, and may be supported in an amount effective for producing ethylene oxide. The cesium content (supported amount) is not particularly limited, but is 500 to 5000 ppm, preferably 1000 to 4000 ppm, based on the mass of the ethylene oxide production catalyst. Within such a range, the reaction for producing ethylene oxide by vapor-phase oxidation of ethylene with a molecular oxygen-containing gas can be effectively promoted.
Rhenium (Re) acts as an auxiliary promoter for cesium. The rhenium content (supported amount) is not particularly limited, but is 50 to 2000 ppm, preferably 100 to 1000 ppm, based on the mass of the ethylene oxide production catalyst. Within such a range, the reaction for producing ethylene oxide by vapor-phase oxidation of ethylene with a molecular oxygen-containing gas can be effectively promoted. In particular, rhenium is considered to be an important factor in terms of catalyst selectivity. For this reason, the selectivity of the catalyst can be effectively improved by controlling the amount of rhenium within the above range. When Re exceeds the above range, not only the selectivity is not increased, but also the reaction temperature needs to be increased, which may adversely affect the life performance.
タングステン（Ｗ）は、レニウムの補助促進剤として作用する。このように各触媒成分が相互に作用することによって、本発明の触媒は、高い選択性を発揮できる。タングステン（Ｗ）の含有量（担持量）は、特に制限されず、エチレンオキシドの製造に有効な量で担持すればよい。タングステンの含有量（担持量）は、特に制限されないが、エチレンオキシド製造用触媒の質量基準で、好ましくは１０〜２０００ｐｐｍであり、より好ましくは５０〜１０００ｐｐｍである。このような範囲であれば、エチレンを分子状酸素含有ガスにより気相酸化してエチレンオキシドを製造する際に、レニウムの効果（触媒の選択性の向上効果）を促進できる。 Tungsten (W) acts as an auxiliary promoter for rhenium. Thus, when each catalyst component interacts, the catalyst of the present invention can exhibit high selectivity. The content (supported amount) of tungsten (W) is not particularly limited, and it may be supported in an amount effective for the production of ethylene oxide. The content (supported amount) of tungsten is not particularly limited, but is preferably 10 to 2000 ppm, more preferably 50 to 1000 ppm, based on the mass of the catalyst for producing ethylene oxide. Within such a range, the effect of rhenium (the effect of improving the selectivity of the catalyst) can be promoted when ethylene oxide is produced by vapor-phase oxidation of ethylene with a molecular oxygen-containing gas.
本発明の触媒は、上記触媒成分に加えて、他の触媒成分を含んでもよい。ここで、他の触媒成分としては、特に制限されないが、例えば、バナジウム、クロム、マンガン、コバルト、ニッケル、銅、ニオブ、モリブデン、スズ、アンチモン、タンタル、ビスマス、チタン、ジルコニウムなどが挙げられる。また、このような他の触媒成分の含有量（担持量）は、本発明による触媒成分の効果を阻害しない限り特に制限されないが、好ましくはエチレンオキシド製造用触媒の質量基準で、１０〜１０００ｐｐｍである。 The catalyst of the present invention may contain other catalyst components in addition to the above catalyst components. Here, the other catalyst components are not particularly limited, and examples thereof include vanadium, chromium, manganese, cobalt, nickel, copper, niobium, molybdenum, tin, antimony, tantalum, bismuth, titanium, and zirconium. Further, the content (supported amount) of such other catalyst component is not particularly limited as long as the effect of the catalyst component according to the present invention is not impaired, but is preferably 10 to 1000 ppm based on the mass of the catalyst for producing ethylene oxide. .
なお上述した触媒の組成や各成分の含有量は、上述した蛍光Ｘ線分析法を用いて決定できる。 The composition of the catalyst and the content of each component described above can be determined using the above-described fluorescent X-ray analysis method.
（触媒の製造方法）
次に、上記したようにして製造された本発明に係る担体を用いて、本発明のエチレンオキシド製造用触媒を製造するが、その製造方法は、上記したような担体を使用する以外は、従来公知のエチレンオキシド製造用触媒の製造方法に従って調製されうる。以下、本発明にかかる好ましい触媒の実施形態を記載する。しかし、本発明は、下記の好ましい実施形態に限定されず、適宜修飾してあるいは他の公知の方法に本発明に係る担体を使用することによって、触媒を製造できる。
(Catalyst production method)
Next, the catalyst for producing ethylene oxide of the present invention is produced using the carrier according to the present invention produced as described above, and the production method thereof is conventionally known except that the carrier as described above is used. It can be prepared according to a method for producing a catalyst for producing ethylene oxide. Hereinafter, preferred embodiments of the catalyst according to the present invention will be described. However, the present invention is not limited to the following preferred embodiments, and a catalyst can be produced by appropriately modifying or using the carrier according to the present invention in other known methods.
まず、各触媒成分の前駆体を適当な溶媒に溶解して、触媒前駆体溶液を調製する。ここで、各触媒成分の前駆体としては、溶媒に溶解する形態であれば特に制限されないが、例えば、銀の場合には、例えば、硝酸銀、炭酸銀、シュウ酸銀、酢酸銀、プロピオン酸銀、乳酸銀、クエン酸銀、ネオデカン酸銀などが挙げられる。これらのうち、シュウ酸銀、硝酸銀が好ましい。セシウムの場合には、セシウムの硝酸塩、亜硝酸塩、炭酸塩、シュウ酸塩、ハロゲン化物、酢酸塩、硫酸塩、過レニウム酸塩、タングステン酸塩などが挙げられる。これらのうち、硝酸セシウム、炭酸セシウム、過レニウム酸セシウム、タングステン酸セシウムが好ましい。レニウムの場合には、過レニウム酸アンモニウム、過レニウム酸ナトリウム、過レニウム酸カリウム、過レニウム酸、塩化レニウム、酸化レニウム、過レニウム酸セシウムなどが挙げられる。これらのうち、過レニウム酸アンモニウム、過レニウム酸セシウムが好ましい。タングステンの場合には、酸化タングステン、タングステン酸、タングステン酸塩、リンタングステン酸、ケイタングステン酸などのヘテロポリ酸および／またはヘテロポリ酸の塩などが挙げられる。これらのうち、メタタングステン酸アンモニウム、メタタングステン酸セシウム、パラタングステン酸アンモニウム、パラタングステン酸セシウム、リンタングステン酸アンモニウム、リンタングステン酸セシウム、ケイタングステン酸アンモニウム、ケイタングステン酸セシウムが好ましい。上記各触媒成分は、単独で使用されてもあるいは２種以上の混合物の形態で使用されてもよい。また、上記各触媒成分の添加量は、上記した所定の触媒組成となるように適宜決定できる。 First, the precursor of each catalyst component is dissolved in an appropriate solvent to prepare a catalyst precursor solution. Here, the precursor of each catalyst component is not particularly limited as long as it is dissolved in a solvent. For example, in the case of silver, for example, silver nitrate, silver carbonate, silver oxalate, silver acetate, silver propionate , Silver lactate, silver citrate, silver neodecanoate and the like. Of these, silver oxalate and silver nitrate are preferred. In the case of cesium, cesium nitrate, nitrite, carbonate, oxalate, halide, acetate, sulfate, perrhenate, tungstate and the like can be mentioned. Of these, cesium nitrate, cesium carbonate, cesium perrhenate, and cesium tungstate are preferable. In the case of rhenium, examples thereof include ammonium perrhenate, sodium perrhenate, potassium perrhenate, perrhenic acid, rhenium chloride, rhenium oxide, cesium perrhenate, and the like. Of these, ammonium perrhenate and cesium perrhenate are preferred. In the case of tungsten, heteropolyacids such as tungsten oxide, tungstic acid, tungstate, phosphotungstic acid, silicotungstic acid and / or salts of heteropolyacids can be used. Of these, ammonium metatungstate, cesium metatungstate, ammonium paratungstate, cesium paratungstate, ammonium phosphotungstate, cesium phosphotungstate, ammonium silicotungstate, and cesium silicotungstate are preferred. Each of the above catalyst components may be used alone or in the form of a mixture of two or more. Moreover, the addition amount of each said catalyst component can be suitably determined so that it may become the above-mentioned predetermined catalyst composition.
上記各触媒成分の前駆体を溶解する溶媒もまた、各触媒成分を溶解できるものであれば特に制限されない。具体的には、水、メタノールおよびエタノールなどのアルコール類、トルエンの芳香族化合物などが挙げられる。これらのうち、水、エタノールが好ましい。 The solvent that dissolves the precursor of each catalyst component is not particularly limited as long as it can dissolve each catalyst component. Specific examples include water, alcohols such as methanol and ethanol, and aromatic compounds of toluene. Of these, water and ethanol are preferred.
ここで、触媒前駆体溶液は、上記触媒成分に加えて、必要に応じて、錯体を形成するための錯化剤をさらに溶媒に添加してもよい。錯化剤としては、特に制限されないが、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、エチレンジアミン、プロピレンジアミンなどが挙げられる。上記錯化剤単独で使用されてもあるいは２種以上の混合物の形態で使用されてもよい。 Here, the catalyst precursor solution may further contain a complexing agent for forming a complex, if necessary, in addition to the catalyst component. The complexing agent is not particularly limited, and examples thereof include monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and propylenediamine. The complexing agent may be used alone or in the form of a mixture of two or more.
次いで、このように調製された触媒前駆体溶液を、上記で準備した担体に含浸させる。ここで、上記触媒前駆体溶液は、触媒前駆体溶液毎に別々に調製して、担体に順次含浸してもあるいは各触媒前駆体を一つの溶媒に溶解して、一つの触媒前駆体溶液とし、これを担体に含浸してもよい。 Next, the support prepared as described above is impregnated with the catalyst precursor solution thus prepared. Here, the catalyst precursor solution may be prepared separately for each catalyst precursor solution and impregnated on the support sequentially, or each catalyst precursor may be dissolved in one solvent to form one catalyst precursor solution. The carrier may be impregnated with this.
続いて、含浸後の担体を乾燥し、焼成する。乾燥は、空気、酸素、または不活性ガス（例えば、窒素）の雰囲気中で、必要であれば減圧下で、８０〜１２０℃の温度で行うことが好ましい。また、焼成は、空気、酸素、または不活性ガス（例えば、窒素）の雰囲気中で、１００〜８００℃の温度で、好ましくは１００〜６００℃の温度で０．１〜１００時間、好ましくは０．１〜１０時間程度行うことである。なお、焼成は、１段階のみ行われてもよいし、２段階以上行われてもよい。好ましい焼成条件としては、１段階目の焼成を空気雰囲気中で１００〜２５０℃にて０．１〜１０時間行い、２段階目の焼成を空気雰囲気中で２５０〜４５０℃にて０．１〜１０時間行う条件が挙げられる。さらに好ましくは、かような空気雰囲気中での焼成後にさらに、不活性ガス（例えば、窒素、ヘリウム、アルゴンなど）雰囲気中で４５０〜８００℃にて０．１〜１０時間、焼成を行ってもよい。 Subsequently, the impregnated carrier is dried and fired. Drying is preferably performed at a temperature of 80 to 120 ° C. in an atmosphere of air, oxygen, or an inert gas (for example, nitrogen) under reduced pressure if necessary. The firing is performed in an atmosphere of air, oxygen, or an inert gas (for example, nitrogen) at a temperature of 100 to 800 ° C., preferably at a temperature of 100 to 600 ° C. for 0.1 to 100 hours, preferably 0. .1 to about 10 hours. In addition, baking may be performed only in one step or may be performed in two or more steps. As preferable firing conditions, the first stage firing is performed in an air atmosphere at 100 to 250 ° C. for 0.1 to 10 hours, and the second stage firing is performed in an air atmosphere at 250 to 450 ° C. for 0.1 to 10 hours. The conditions for 10 hours are mentioned. More preferably, after firing in such an air atmosphere, firing may be performed at 450 to 800 ° C. for 0.1 to 10 hours in an inert gas (eg, nitrogen, helium, argon, etc.) atmosphere. Good.
このようにして得られた本発明の触媒は、選択性および触媒寿命（耐久性）に優れる。したがって、本発明のエチレンオキシド製造用触媒を使用することによって、エチレンオキシドを長期に亘って高選択率で製造でき、産業上非常に有益である。 The catalyst of the present invention thus obtained is excellent in selectivity and catalyst life (durability). Therefore, by using the catalyst for producing ethylene oxide of the present invention, ethylene oxide can be produced with high selectivity over a long period of time, which is very useful industrially.
ゆえに、本発明はまた、本発明の触媒の存在下に分子状酸素含有ガスを用いエチレンを気相酸化するエチレンオキシドの製造方法もまた提供される。 Therefore, the present invention also provides a method for producing ethylene oxide in which ethylene is vapor-phase oxidized using a molecular oxygen-containing gas in the presence of the catalyst of the present invention.
（エチレンオキシドの製造方法）
本発明のエチレンオキシドの製造方法は、触媒として本発明のエチレンオキシド製造用触媒を使用する点を除けば、常法に従って行われうる。
(Method for producing ethylene oxide)
The method for producing ethylene oxide of the present invention can be carried out according to a conventional method except that the catalyst for producing ethylene oxide of the present invention is used as a catalyst.
例えば、工業的製造規模における一般的な条件、すなわち反応温度１５０〜３００℃、好ましくは１８０〜２８０℃、反応圧力０．２〜４ＭＰａＧ、好ましくは０．９〜３ＭＰａＧであり、空間速度は１，０００〜３０，０００ｈ−１（ＳＴＰ）、好ましくは３，０００〜８，０００ｈ−１（ＳＴＰ）である。 For example, general conditions on an industrial production scale, that is, a reaction temperature of 150 to 300 ° C., preferably 180 to 280 ° C., a reaction pressure of 0.2 to 4 MPaG, preferably 0.9 to 3 MPaG, and a space velocity is 1, 000 to 30,000 h −1 (STP), preferably 3,000 to 8,000 h −1 (STP).
触媒に接触させる原料ガスとしては、エチレン０．５〜４０容量％、酸素３〜１０容量％、炭酸ガス１〜３０容量％、残部の窒素、アルゴン、水蒸気等の不活性ガスおよびメタン、エタン等の低級炭化水素類からなり、さらに反応抑制剤としてのエチルクロライド、エチレンジクロライド、ビニルクロライド、メチルクロライドなどの有機塩素化合物を０．１〜１０容量ｐｐｍ含有するものが挙げられる。本発明の製造方法において使用される分子状酸素含有ガスとしては、空気、酸素および富化空気が挙げられる。 The raw material gas to be brought into contact with the catalyst is 0.5 to 40% by volume of ethylene, 3 to 10% by volume of oxygen, 1 to 30% by volume of carbon dioxide, the remaining inert gas such as nitrogen, argon and water vapor, methane, ethane, etc. And those containing 0.1 to 10 ppm by volume of an organic chlorine compound such as ethyl chloride, ethylene dichloride, vinyl chloride, and methyl chloride as a reaction inhibitor. Examples of the molecular oxygen-containing gas used in the production method of the present invention include air, oxygen, and enriched air.
本発明の効果を、以下の実施例および比較例を用いて説明する。ただし、本発明の効果を奏するものであれば、本発明の技術的範囲が以下の実施例のみに制限されるわけではない。以下に実施例、比較例に用いた各測定法について説明する。 The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples as long as the effects of the present invention are achieved. Below, each measuring method used for the Example and the comparative example is demonstrated.
（担体のＢＥＴ比表面積の測定）
担体を粉砕した後、０．８５〜１．２ｍｍの粒径に分級したもの約０．２ｇを正確に秤量した。秤量したサンプルを２００℃にて少なくとも３０分間脱気し、ＢＥＴ（Ｂｒｕｎａｕｅｒ−Ｅｍｍｅｔ−Ｔｅｌｌｅｒ）法により測定した。
(Measurement of BET specific surface area of support)
After pulverizing the carrier, about 0.2 g classified to a particle size of 0.85 to 1.2 mm was accurately weighed. The weighed sample was deaerated at 200 ° C. for at least 30 minutes and measured by the BET (Brunauer-Emmet-Teller) method.
（担体中のアルカリ金属及びシリカ（ＳｉＯ２）含有量の測定）
蛍光Ｘ線分析法を用いて行った。測定装置としてＲＩＧＡＫＵ製ＲＩＸ２０００を用い、ファンダメンタルパラメータ法（ＦＰ法）にて測定した。
(Measurement of alkali metal and silica (SiO 2 ) content in support)
This was performed using fluorescent X-ray analysis. RIX2000 manufactured by RIGAKU was used as a measuring apparatus, and measurement was performed by a fundamental parameter method (FP method).
（担体の吸水率の測定）
日本工業規格（ＪＩＳ Ｒ ２２０５（１９９８））に記載の方法に準拠して、以下の手法により測定した。
ａ）担体を１２０℃に保温した乾燥機中に入れ、恒量に達した際の質量を秤量した（乾燥質量：Ｗ１（ｇ））。
ｂ）上記ａ）で秤量した担体を水中に沈めて３０分間以上煮沸した後、室温の水中にて冷却し、飽水サンプルとした。
ｃ）上記ｂ）で得た飽水サンプルを水中から取り出し、湿布ですばやく表面を拭い、水滴を除去した後に秤量した（飽水サンプル質量：Ｗ２（ｇ））。
ｄ）上記で得られたＷ１およびＷ２を用い、下記数式１に従って、吸水率を算出した。
(Measurement of water absorption rate of carrier)
In accordance with the method described in Japanese Industrial Standard (JIS R 2205 (1998)), the measurement was performed by the following method.
a) The carrier was put in a drier kept at 120 ° C., and the mass when reaching a constant weight was measured (dry mass: W1 (g)).
b) The carrier weighed in a) above was submerged in water and boiled for 30 minutes or more, and then cooled in room temperature water to obtain a saturated sample.
c) The saturated sample obtained in the above b) was taken out from the water, and the surface was quickly wiped with a compress, and after removing water droplets, weighed (saturated sample mass: W2 (g)).
d) The water absorption was calculated according to the following formula 1 using W1 and W2 obtained above.
カラムとしてＩｏｎ Ｐａｃ ＣＳ１２Ａ、サプレッサーとしてＣＳＲＳ−３００を備えたイオンクロマトグラフ装置ＤＸ−５００（何れもダイオネクス製）を用いた。溶離液としては２０ｍｍｏｌ／Ｌ−メタンスルホン酸を用い、カラムオーブン温度を３０℃に保持した上で、上記条件（１）および（２）により調整された水溶液を５０μＬ分取して測定した。当該水溶液のナトリウムおよびセシウム含有量は、予め作成しておいた対応する元素の検量線を基準に算出され、この水溶液のナトリウムおよびセシウム含有量を元に触媒１ｇあたりの水溶出性ナトリウムおよび水溶出性セシウム量を計算した。なお、これらの水溶出性ナトリウム量および水溶出性セシウム量は、例えば原子吸光法やＩＣＰ発光分析よって測定することも可能である。
An ion chromatograph apparatus DX-500 (all manufactured by Dionex) equipped with Ion Pac CS12A as a column and CSRS-300 as a suppressor was used. As the eluent, 20 mmol / L-methanesulfonic acid was used, and the column oven temperature was kept at 30 ° C., and 50 μL of the aqueous solution prepared according to the above conditions (1) and (2) was taken and measured. The sodium and cesium contents of the aqueous solution are calculated on the basis of a calibration curve for the corresponding element prepared in advance. Based on the sodium and cesium contents of the aqueous solution, the water elution sodium and water elution per gram of the catalyst The amount of sex cesium was calculated. The amount of water-eluting sodium and the amount of water-eluting cesium can also be measured by, for example, atomic absorption method or ICP emission analysis.
（実施例１）
以下に、触媒Ａの調製手順を示す。シュウ酸銀１４．６ｇ、硝酸セシウム０．２５６３ｇ、過レニウム酸アンモニウム０．０４５７ｇ、メタタングステン酸アンモニウム０．０３０８ｇを、約１５ｍＬの水に溶解し、さらに錯化剤としてエチレンジアミン６．８ｍＬを加え、触媒前駆体溶液Ａを調製した。
Example 1
Below, the preparation procedure of the catalyst A is shown. 14.6 g of silver oxalate, 0.2563 g of cesium nitrate, 0.0457 g of ammonium perrhenate, and 0.0308 g of ammonium metatungstate are dissolved in about 15 mL of water, and 6.8 mL of ethylenediamine is added as a complexing agent. Catalyst precursor solution A was prepared.
この触媒前駆体溶液Ａを、担体Ａ（α−アルミナ担体、ＢＥＴ比表面積＝０．７２ｍ２／ｇ、ＳｉＯ２含有量＝２．２８質量％、Ｎａ２Ｏ含有量＝０．２１質量％、吸水率＝４４．３％、細孔容積＝０．４４ｍＬ／ｇ）５２．２ｇに含浸した後、９０℃で減圧乾燥した。これを空気気流中３００℃で０．２５時間熱処理した後、窒素気流中５７０℃で３時間熱処理して触媒Ａを得た。 This catalyst precursor solution A was mixed with carrier A (α-alumina carrier, BET specific surface area = 0.72 m 2 / g, SiO 2 content = 2.28 mass%, Na 2 O content = 0.21 mass%, After impregnating 52.2 g (water absorption rate = 44.3%, pore volume = 0.44 mL / g), it was dried at 90 ° C. under reduced pressure. This was heat-treated at 300 ° C. for 0.25 hours in an air stream, and then heat-treated at 570 ° C. for 3 hours in a nitrogen stream to obtain Catalyst A.
このようにして調製された触媒Ａの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．８質量％、Ｃｓ（Ｃｓ換算）＝２８１０質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４６０質量ｐｐｍ、Ｗ（Ｗ換算）＝３６０質量ｐｐｍであった。 The content of each component of the catalyst A thus prepared (mass basis of the catalyst) is: Ag (silver conversion) = 14.8 mass%, Cs (Cs conversion) = 2810 mass ppm, Re (Re conversion) = 460 mass ppm, W (W conversion) = 360 mass ppm.
（実施例２）
以下に、触媒Ｂの調製手順を示す。シュウ酸銀１４．６ｇ、硝酸セシウム０．２７７７ｇ、過レニウム酸アンモニウム０．０４５７ｇ、メタタングステン酸アンモニウム０．０３０８ｇを、約１５ｍＬの水に溶解し、さらに錯化剤としてエチレンジアミン６．８ｍＬを加え、触媒前駆体溶液Ｂを調製した。
(Example 2)
Below, the preparation procedure of the catalyst B is shown. 14.6 g of silver oxalate, 0.2777 g of cesium nitrate, 0.0457 g of ammonium perrhenate, 0.0308 g of ammonium metatungstate are dissolved in about 15 mL of water, and 6.8 mL of ethylenediamine is further added as a complexing agent. Catalyst precursor solution B was prepared.
この触媒前駆体溶液Ｂを、担体Ｂ（α−アルミナ担体、ＢＥＴ比表面積＝０．８０ｍ２／ｇ、ＳｉＯ２含有量＝２．２６質量％、Ｎａ２Ｏ含有量＝０．１８質量％、吸水率＝４４．０％、細孔容積＝０．４４ｍＬ／ｇ）５２．２ｇに含浸した後、９０℃で減圧乾燥した。これを空気気流中３００℃で０．２５時間熱処理した後、窒素気流中５７０℃で３時間熱処理して触媒Ｂを得た。 This catalyst precursor solution B was mixed with carrier B (α-alumina carrier, BET specific surface area = 0.80 m 2 / g, SiO 2 content = 2.26% by mass, Na 2 O content = 0.18% by mass, After impregnating 52.2 g (water absorption rate = 44.0%, pore volume = 0.44 mL / g), it was dried at 90 ° C. under reduced pressure. This was heat-treated at 300 ° C. for 0.25 hours in an air stream, and then heat-treated at 570 ° C. for 3 hours in a nitrogen stream to obtain Catalyst B.
このようにして調製された触媒Ｂの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．８質量％、Ｃｓ（Ｃｓ換算）＝３０５０質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４６０質量ｐｐｍ、Ｗ（Ｗ換算）＝３６０質量ｐｐｍであった。 The content of each component of the catalyst B thus prepared (mass basis of the catalyst) is: Ag (silver equivalent) = 14.8 mass%, Cs (Cs equivalent) = 3050 mass ppm, Re (Re equivalent) = 460 mass ppm, W (W conversion) = 360 mass ppm.
（実施例３）
以下に、触媒Ｃの調製手順を示す。シュウ酸銀１４．６ｇ、硝酸セシウム０．２７７７ｇ、過レニウム酸アンモニウム０．０４５７ｇ、メタタングステン酸アンモニウム０．０３０８ｇを、約１５ｍＬの水に溶解し、さらに錯化剤としてエチレンジアミン６．８ｍＬを加え、触媒前駆体溶液Ｃを調製した。
(Example 3)
Below, the preparation procedure of the catalyst C is shown. 14.6 g of silver oxalate, 0.2777 g of cesium nitrate, 0.0457 g of ammonium perrhenate, 0.0308 g of ammonium metatungstate are dissolved in about 15 mL of water, and 6.8 mL of ethylenediamine is further added as a complexing agent. A catalyst precursor solution C was prepared.
この触媒前駆体溶液Ｃを、担体Ｃ（α−アルミナ担体、ＢＥＴ比表面積＝０．６６ｍ２／ｇ、ＳｉＯ２含有量＝２．３３質量％、Ｎａ２Ｏ含有量＝０．４１質量％、吸水率＝４１．２％、細孔容積＝０．３９ｍＬ／ｇ）５２．２ｇに含浸した後、９０℃で減圧乾燥した。これを空気気流中３００℃で０．２５時間熱処理した後、窒素気流中５７０℃で３時間熱処理して触媒Ｃを得た。 This catalyst precursor solution C was mixed with support C (α-alumina support, BET specific surface area = 0.66 m 2 / g, SiO 2 content = 2.33 mass%, Na 2 O content = 0.41 mass%, After impregnating 52.2 g (water absorption rate = 41.2%, pore volume = 0.39 mL / g), it was dried under reduced pressure at 90 ° C. This was heat-treated at 300 ° C. for 0.25 hours in an air stream, and then heat-treated at 570 ° C. for 3 hours in a nitrogen stream to obtain Catalyst C.
このようにして調製された触媒Ｃの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．８質量％、Ｃｓ（Ｃｓ換算）＝３０５０質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４６０質量ｐｐｍ、Ｗ（Ｗ換算）＝３６０質量ｐｐｍであった。 The content of each component of the catalyst C thus prepared (catalyst mass standard) is: Ag (silver conversion) = 14.8 mass%, Cs (Cs conversion) = 3050 mass ppm, Re (Re conversion) = 460 mass ppm, W (W conversion) = 360 mass ppm.
（比較例１）
以下に、触媒Ｄの調製手順を示す。シュウ酸銀１４．６ｇ、硝酸セシウム０．２３５０ｇ、過レニウム酸アンモニウム０．０４５７ｇ、メタタングステン酸アンモニウム０．０３０８ｇを、約１４ｍＬの水に溶解し、さらに錯化剤としてエチレンジアミン６．８ｍＬを加え、触媒前駆体溶液Ｄを調製した。
(Comparative Example 1)
Below, the preparation procedure of the catalyst D is shown. 14.6 g of silver oxalate, 0.2350 g of cesium nitrate, 0.0457 g of ammonium perrhenate, and 0.0308 g of ammonium metatungstate are dissolved in about 14 mL of water, and 6.8 mL of ethylenediamine is added as a complexing agent. A catalyst precursor solution D was prepared.
この触媒前駆体溶液Ｄを、担体Ｄ（α−アルミナ担体、ＢＥＴ比表面積＝０．６３ｍ２／ｇ、ＳｉＯ２含有量＝２．２０質量％、Ｎａ２Ｏ含有量＝０．５２質量％、吸水率＝４０．１％、細孔容積＝０．４１ｍＬ／ｇ）５２．２ｇに含浸した後、９０℃で減圧乾燥した。これを空気気流中３００℃で０．２５時間熱処理した後、窒素気流中５７０℃で３時間熱処理して触媒Ｄを得た。 This catalyst precursor solution D was mixed with carrier D (α-alumina carrier, BET specific surface area = 0.63 m 2 / g, SiO 2 content = 2.20 mass%, Na 2 O content = 0.52 mass%, After impregnating 52.2 g (water absorption rate = 40.1%, pore volume = 0.41 mL / g), it was dried at 90 ° C. under reduced pressure. This was heat-treated at 300 ° C. for 0.25 hours in an air stream, and then heat-treated at 570 ° C. for 3 hours in a nitrogen stream to obtain Catalyst D.
このようにして調製された触媒Ｄの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．８質量％、Ｃｓ（Ｃｓ換算）＝２５８０質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４６０質量ｐｐｍ、Ｗ（Ｗ換算）＝３６０質量ｐｐｍであった。 The content of each component of the catalyst D thus prepared (catalyst mass standard) is: Ag (silver equivalent) = 14.8 mass%, Cs (Cs equivalent) = 2580 mass ppm, Re (Re equivalent) = 460 mass ppm, W (W conversion) = 360 mass ppm.
（比較例２）
以下に、触媒Ｅの調製手順を示す。シュウ酸銀１４．６ｇ、硝酸セシウム０．１２８２ｇ、過レニウム酸アンモニウム０．０４５７ｇ、メタタングステン酸アンモニウム０．０３０８ｇを、約１３ｍＬの水に溶解し、さらに錯化剤としてエチレンジアミン６．８ｍＬを加え、触媒前駆体溶液Ｅを調製した。
(Comparative Example 2)
Below, the preparation procedure of the catalyst E is shown. 14.6 g of silver oxalate, 0.1282 g of cesium nitrate, 0.0457 g of ammonium perrhenate, 0.0308 g of ammonium metatungstate are dissolved in about 13 mL of water, and 6.8 mL of ethylenediamine is added as a complexing agent. A catalyst precursor solution E was prepared.
この触媒前駆体溶液Ｅを、担体Ｅ（α−アルミナ担体、ＢＥＴ比表面積＝１．８０ｍ２／ｇ、ＳｉＯ２含有量＝２．３４質量％、Ｎａ２Ｏ含有量は存在せず、蛍光Ｘ線分析による検出限界未満、吸水率＝４０．１％、細孔容積＝０．４１ｍＬ／ｇ）５２．２ｇに含浸した後、９０℃で減圧乾燥した。これを空気気流中３００℃で０．２５時間熱処理した後、窒素気流中５７０℃で３時間熱処理して触媒Ｅを得た。 This catalyst precursor solution E was used as carrier E (α-alumina carrier, BET specific surface area = 1.80 m 2 / g, SiO 2 content = 2.34% by mass, no Na 2 O content, fluorescent X After impregnating 52.2 g (below the detection limit by line analysis, water absorption = 40.1%, pore volume = 0.41 mL / g), it was dried at 90 ° C. under reduced pressure. This was heat-treated at 300 ° C. for 0.25 hours in an air stream, and then heat-treated at 570 ° C. for 3 hours in a nitrogen stream to obtain Catalyst E.
このようにして調製された触媒Ｅの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．８質量％、Ｃｓ（Ｃｓ換算）＝１４００質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４６０質量ｐｐｍ、Ｗ（Ｗ換算）＝３６０質量ｐｐｍであった。 The content of each component of the catalyst E thus prepared (catalyst mass standard) is: Ag (silver equivalent) = 14.8 mass%, Cs (Cs equivalent) = 1400 mass ppm, Re (Re equivalent) = 460 mass ppm, W (W conversion) = 360 mass ppm.
実施例１〜３ならびに比較例１および２にかかる触媒についての水溶出性Ｎａ量、水溶出性Ｃｓ量、水溶出性Ｎａ量に対する水溶出性Ｃｓ量のモル比（Ｃｓ／Ｎａモル比）を担体のＢＥＴ比表面積で除した値、並びに当該触媒を反応に用いたときのエチレンオキシド選択率および反応温度を表１に示した。 For the catalysts according to Examples 1 to 3 and Comparative Examples 1 and 2, the water-eluting Na amount, the water-eluting Cs amount, and the molar ratio of the water-eluting Cs amount to the water-eluting Na amount (Cs / Na molar ratio) Table 1 shows values obtained by dividing the BET specific surface area of the support, ethylene oxide selectivity and reaction temperature when the catalyst was used in the reaction.
（触媒性能評価）
上記実施例１から３ならびに比較例１および２で製造された触媒Ａ〜Ｅを、それぞれ、０．６０〜０．８５ｍｍに破砕した。次に、破砕した触媒３．０ｇを、それぞれ、内径５ｍｍ、管長３００ｍｍの外部が加熱式の二重管式ステンレス製反応器に充填し、この充填層にエチレン２４容量％、酸素７．０容量％、二酸化炭素２．０容量％、エチルクロライド２．６容量ｐｐｍ、残余が窒素からなるガスを導入し、１．６ＭＰａＧで、空間速度５５００ｈ−１の条件で、エチレン転化率が１０．４モル％となるようにして反応を行った。下記数式２および数式３に従って、エチレンオキシド製造時の転化率（数式２）および選択率（数式３）を算出した。各触媒の性能を下記表１に示す。
(Catalyst performance evaluation)
Catalysts A to E produced in Examples 1 to 3 and Comparative Examples 1 and 2 were each crushed to 0.60 to 0.85 mm. Next, 3.0 g of the crushed catalyst was charged into a heating type double tube stainless steel reactor having an inner diameter of 5 mm and a tube length of 300 mm, respectively, and this packed bed was 24% by volume of ethylene and 7.0% by volume of oxygen. %, Carbon dioxide 2.0% by volume, ethyl chloride 2.6 ppm by volume, and the balance nitrogen gas is introduced, and the ethylene conversion rate is 10.4 mol under the conditions of 1.6 MPaG and space velocity 5500 h −1. The reaction was carried out so that the concentration became%. According to the following formula 2 and formula 3, the conversion rate (formula 2) and the selectivity (formula 3) during ethylene oxide production were calculated. The performance of each catalyst is shown in Table 1 below.
本発明は、エチレンを酸化しエチレンオキシドを製造する技術に用いる触媒を提供するとともに、エチレンオキシドを製造することができる方法を提供するものである。 The present invention provides a catalyst used in a technique for producing ethylene oxide by oxidizing ethylene, and also provides a method capable of producing ethylene oxide.
Claims (6)
（１）触媒３．０ｇを１００ｍｌの純水に投入し１００℃で３０分間煮沸した後、液１を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸した後、液２を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸し、液３を除く。
（２）液１〜３を集めて、２００ｍｌに調整する。
（３）当該調整した液を陽イオンクロマトグラフィーにより、水溶出性ナトリウムの濃度を測定する。 A catalyst in which silver is a catalytically active component, cesium is a cocatalyst component, and the α-alumina support containing sodium carries the catalytically active component and the cocatalyst component. The catalyst for ethylene oxide production characterized by being 1.0 to 11.5 μmol (per gram of catalyst).
(1) After adding 3.0 g of catalyst to 100 ml of pure water and boiling at 100 ° C. for 30 minutes, liquid 1 was removed, 100 ml of pure water was added again and boiling at 100 ° C. for 30 minutes, and then liquid 2 was added. In addition, 100 ml of pure water is newly added and boiled at 100 ° C. for 30 minutes to remove liquid 3.
(2) Collect liquids 1-3 and adjust to 200 ml.
(3) The concentration of water-eluting sodium is measured by cation chromatography on the adjusted liquid.
（１）触媒３．０ｇを１００ｍｌの純水に投入し１００℃で３０分間煮沸した後、液１を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸した後、液２を除き、更に新たに純水１００ｍｌを投入し１００℃で３０分間煮沸し、液３を除く。
（２）液１〜３を集めて、２００ｍｌに調整する。
（３）当該調整した液を陽イオンクロマトグラフィーにより、水溶出性セシウムの濃度を測定する。 A catalyst in which silver is a catalytically active component, cesium is a promoter component, and the catalyst-active component and the promoter component are supported on an α-alumina carrier containing sodium, and the water-eluting cesium measured under the following conditions is The catalyst for ethylene oxide production characterized by being 4.5 to 7.4 μmol (per gram of catalyst).
(1) After adding 3.0 g of catalyst to 100 ml of pure water and boiling at 100 ° C. for 30 minutes, liquid 1 was removed, 100 ml of pure water was added again and boiling at 100 ° C. for 30 minutes, and then liquid 2 was added. In addition, 100 ml of pure water is newly added and boiled at 100 ° C. for 30 minutes to remove liquid 3.
(2) Collect liquids 1-3 and adjust to 200 ml.
(3) The concentration of water-eluting cesium is measured by cation chromatography on the adjusted liquid.
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