JP2016193391A - Catalyst for producing alkylene oxide and method for producing alkylene oxide - Google Patents
Catalyst for producing alkylene oxide and method for producing alkylene oxide Download PDFInfo
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- JP2016193391A JP2016193391A JP2015073690A JP2015073690A JP2016193391A JP 2016193391 A JP2016193391 A JP 2016193391A JP 2015073690 A JP2015073690 A JP 2015073690A JP 2015073690 A JP2015073690 A JP 2015073690A JP 2016193391 A JP2016193391 A JP 2016193391A
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- Prior art keywords
- catalyst
- mass
- alkylene oxide
- carrier
- promoter
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- 239000003054 catalyst Substances 0.000 title claims abstract description 222
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 31
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 30
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 30
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 239000010937 tungsten Substances 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- 229910001882 dioxygen Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical group C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 230000000694 effects Effects 0.000 description 21
- 239000011148 porous material Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 150000003377 silicon compounds Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000002245 particle 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 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
- 241000282376 Panthera tigris Species 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
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229940100890 silver compound Drugs 0.000 description 3
- 150000003379 silver compounds Chemical class 0.000 description 3
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- 244000144730 Amygdalus persica Species 0.000 description 2
- 241000208223 Anacardiaceae Species 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000758791 Juglandaceae Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 235000009827 Prunus armeniaca Nutrition 0.000 description 2
- 244000018633 Prunus armeniaca Species 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 description 2
- FMWMEQINULDRBI-UHFFFAOYSA-L copper;sulfite Chemical compound [Cu+2].[O-]S([O-])=O FMWMEQINULDRBI-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 235000014571 nuts Nutrition 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003388 sodium compounds Chemical class 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
- 150000004684 trihydrates Chemical class 0.000 description 2
- 235000020234 walnut Nutrition 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- PFKAKHILNWLJRT-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PFKAKHILNWLJRT-UHFFFAOYSA-H 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
- PURTUPNWTLPILZ-UHFFFAOYSA-N 2-hydroxypropanoic acid;nickel Chemical compound [Ni].CC(O)C(O)=O.CC(O)C(O)=O PURTUPNWTLPILZ-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
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229920002261 Corn starch Polymers 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
- 239000012692 Fe precursor Substances 0.000 description 1
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
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- 239000012876 carrier material Substances 0.000 description 1
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- GCKQKOCZMXVVKF-UHFFFAOYSA-H cobalt(3+) oxalate Chemical compound [Co+3].[Co+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GCKQKOCZMXVVKF-UHFFFAOYSA-H 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
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- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm 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
- 230000007246 mechanism Effects 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
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- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- LONQOCRNVIZRSA-UHFFFAOYSA-L nickel(2+);sulfite Chemical compound [Ni+2].[O-]S([O-])=O LONQOCRNVIZRSA-UHFFFAOYSA-L 0.000 description 1
- ZVHHIDVFSYXCEW-UHFFFAOYSA-L nickel(ii) nitrite Chemical compound [Ni+2].[O-]N=O.[O-]N=O ZVHHIDVFSYXCEW-UHFFFAOYSA-L 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
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 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
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 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
- 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
- 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
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 150000004764 thiosulfuric acid derivatives Chemical class 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
- 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
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、アルキレンオキシド製造用触媒およびアルキレンオキシドの製造方法に関する。詳細には、本発明は、耐久性に優れ、長期にわたって安定してアルキレンオキシド、特にエチレンオキシド（酸化エチレン）を製造しうるアルキレンオキシド製造用触媒およびアルキレンオキシドの製造方法に関する。 The present invention relates to an alkylene oxide production catalyst and an alkylene oxide production method. Specifically, the present invention relates to a catalyst for producing alkylene oxide, which is excellent in durability and can produce alkylene oxide, particularly ethylene oxide (ethylene oxide) stably over a long period of time, and a method for producing alkylene oxide.
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.
例えば、アルカリ金属とレニウムとを促進剤として併用することにより、触媒の選択性を向上させることができる。特許文献１には、銀と、レニウムと、セシウムのようなアルカリ金属を含む他の金属とをα−アルミナ担体に担持させたエチレンオキシド製造用触媒が開示されている。 For example, the selectivity of the catalyst can be improved by using an alkali metal and rhenium in combination as an accelerator. Patent Document 1 discloses a catalyst for producing ethylene oxide in which silver, rhenium, and another metal containing an alkali metal such as cesium are supported on an α-alumina carrier.
しかしながら、上記特許文献１に記載されるようなレニウムを添加した触媒では、触媒の耐久性が十分ではないという問題があった。触媒が低活性であったり、触媒の劣化が速いと、装置の運転上限温度による制限で製造を継続できなくなり、触媒を短期間で交換する必要がある。 However, the catalyst added with rhenium as described in Patent Document 1 has a problem that the durability of the catalyst is not sufficient. If the catalyst has low activity or the catalyst is rapidly deteriorated, the production cannot be continued due to the limitation due to the operating upper limit temperature of the apparatus, and it is necessary to replace the catalyst in a short period of time.
したがって、本発明は、上記事情を鑑みてなされたものであり、長期間安定してアルキレンオキシドを製造することができる、アルキレンオキシド製造用触媒を提供することを目的とする。 Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an alkylene oxide production catalyst capable of producing an alkylene oxide stably for a long period of time.
本発明者らは、上記の問題を解決すべく、鋭意研究を行った結果、銀、セシウム、およびレニウムを含む触媒において、バナジウム、モリブデン、タングステン、および硫黄からなる群から選択される第１共促進剤と、銅、ニッケル、鉄、およびコバルトからなる群から選択される第２共促進剤とを併せて用いることによって、高い選択性を維持しつつ、触媒寿命が改善されたアルキレンオキシド製造用触媒が得られることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a catalyst containing silver, cesium, and rhenium is selected from the group consisting of vanadium, molybdenum, tungsten, and sulfur. By using an accelerator and a second co-promoter selected from the group consisting of copper, nickel, iron, and cobalt in combination for producing alkylene oxide with improved catalyst life while maintaining high selectivity The inventors found that a catalyst was obtained and completed the present invention.
すなわち、上記目的は、α−アルミナを主成分とする担体に、銀、セシウム、レニウム、第１共促進剤、および第２共促進剤を含む触媒成分を担持してなるアルキレンオキシド製造用触媒であって、前記第１共促進剤は、バナジウム、モリブデン、タングステン、および硫黄からなる群から選択される少なくとも１種であり、前記第２共促進剤は、銅、ニッケル、鉄、およびコバルトからなる群から選択される少なくとも１種である、アルキレンオキシド製造用触媒によって達成される。 That is, the above object is an alkylene oxide production catalyst comprising a carrier mainly composed of α-alumina and carrying a catalyst component containing silver, cesium, rhenium, a first co-promoter, and a second co-promoter. The first co-promoter is at least one selected from the group consisting of vanadium, molybdenum, tungsten, and sulfur, and the second co-promoter is made of copper, nickel, iron, and cobalt. This is achieved by a catalyst for producing an alkylene oxide, which is at least one selected from the group.
本発明のアルキレンオキシド製造用触媒は、選択性および触媒寿命に優れる。したがって、本発明の触媒を用いることにより、高い選択率で長期にわたって安定してアルキレンオキシドを製造できる。 The catalyst for producing an alkylene oxide of the present invention is excellent in selectivity and catalyst life. Therefore, by using the catalyst of the present invention, an alkylene oxide can be produced stably with a high selectivity over a long period of time.
本発明は、α−アルミナを主成分とする担体に、銀、セシウム、レニウム、第１共促進剤、および第２共促進剤を含む触媒成分を担持してなるアルキレンオキシド製造用触媒であって、前記第１共促進剤は、バナジウム、モリブデン、タングステン、および硫黄からなる群から選択される少なくとも１種であり、前記第２共促進剤は、銅、ニッケル、鉄、およびコバルトからなる群から選択される少なくとも１種である、アルキレンオキシド製造用触媒を提供する。 The present invention is an alkylene oxide production catalyst comprising a carrier mainly composed of α-alumina and carrying a catalyst component containing silver, cesium, rhenium, a first co-promoter, and a second co-promoter. The first co-promoter is at least one selected from the group consisting of vanadium, molybdenum, tungsten, and sulfur, and the second co-promoter is from the group consisting of copper, nickel, iron, and cobalt. Provided is a catalyst for producing an alkylene oxide, which is at least one selected.
本発明のアルキレンオキシド製造用触媒は、高い選択性を有するとともに、触媒寿命を有意に改善できる。したがって、本発明のアルキレンオキシド製造用触媒を用いることにより、長期間安定してアルキレンオキシド（特に、エチレンオキシド）を製造することができる。また、触媒交換コストおよびその際の製造停止、プラントの始動、停止などに伴う操業ロスの削減による経済性向上に加え、ＣＯ２排出量削減による環境負荷低減も可能である。 The alkylene oxide production catalyst of the present invention has high selectivity and can significantly improve the catalyst life. Therefore, by using the alkylene oxide production catalyst of the present invention, alkylene oxide (particularly ethylene oxide) can be produced stably for a long period of time. Further, in addition to improving the economic efficiency by reducing the operation loss associated with the catalyst replacement cost and the production stoppage, starting and stopping of the plant at that time, it is also possible to reduce the environmental load by reducing the CO 2 emission amount.
一般的に、触媒の選択性と触媒寿命は、相反する関係にある。このため、選択性および触媒寿命の双方に優れるアルキレンオキシド製造用触媒について、従来、様々な研究がなされてきたにもかかわらず、なかなか実現されていないのが現状である。エチレンオキシドの生産規模は、年間１８００万トンと、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、より優れた触媒性能（選択性及び触媒寿命）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。 In general, catalyst selectivity and catalyst life are in conflict. For this reason, the present situation is that it has not been realized in spite of various studies on the alkylene oxide production catalyst having both excellent selectivity and catalyst life. The production scale of ethylene oxide is very large at 18 million tons per year. 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 catalyst performance (selectivity and catalyst life) has been a continuous theme for researchers in the technical field.
また、触媒の分野では、一般的に、担体の物性や組成ならびに触媒成分の種類や量の組合せにより、触媒は異なる性能を示すことが知られており、所望の性能に合致する組合せを見出すことは困難である。ここで、銀、セシウム（Ｃｓ）およびレニウム（Ｒｅ）を含む触媒（Ａｇ／Ｃｓ／Ｒｅ触媒）は、銀およびセシウムを含む触媒（Ａｇ／Ｃｓ触媒）に比して、選択率が向上する。一方、このようなＡｇ／Ｃｓ／Ｒｅ触媒は、Ｒｅを含まない場合と比較して、短期間で触媒作用が低下する。本発明者らは、上記問題を解決するために鋭意検討を行った結果、所定の第１共促進剤および第２共促進剤を使用することにより、銀、セシウムおよびレニウムを含む触媒の耐久性を有意に向上できることを見出した。 In the field of catalysts, it is generally known that the catalyst exhibits different performances depending on the combination of the physical properties and composition of the support and the types and amounts of the catalyst components. It is difficult. Here, the selectivity of the catalyst containing silver, cesium (Cs) and rhenium (Re) (Ag / Cs / Re catalyst) is improved as compared with the catalyst containing silver and cesium (Ag / Cs catalyst). On the other hand, such an Ag / Cs / Re catalyst has a reduced catalytic action in a short period of time compared to the case where no Re is contained. As a result of intensive studies to solve the above problems, the inventors of the present invention have achieved the durability of a catalyst containing silver, cesium and rhenium by using a predetermined first co-promoter and second co-promoter. It was found that can be improved significantly.
すなわち、本発明の触媒は、銀、セシウム（Ｃｓ）、レニウム（Ｒｅ）、ならびにバナジウム（Ｖ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、および硫黄（Ｓ）からなる群から選択される第１共促進剤ならびに銅（Ｃｕ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）、およびコバルト（Ｃｏ）からなる群から選択される第２促進剤を触媒成分として含む。上述したように、上記触媒成分のうち、レニウムは、優れた選択性を与える反面、短時間で触媒作用が低下する。ここで所定の第１共促進剤を使用することにより、レニウムの触媒機能を維持することができるが、一方で、反応温度が上昇してしまう。しかしながら、本発明者らは、所定の第２共促進剤を用いることによって、触媒活性が向上し、反応温度の上昇が抑制でき、したがって触媒寿命が向上しうることを初めて見出した。このような効果が達成される機構は不明ではあるが、以下のように推測される。なお、本発明は下記推測によって限定されるものではない。すなわち、バナジウム、モリブデン、タングステン、または硫黄は、レニウムの補助促進剤として作用し、レニウムの触媒作用の低下を抑制し高選択性を維持するものと考えられる。しかしながら、第１共促進剤が存在することで触媒活性が低下し、反応温度が上昇してしまう。これに対して、銅、ニッケル、鉄、またはコバルトが存在すると、レニウムおよび第１共促進剤の効果が維持されると同時に、触媒活性が大幅に向上するため、経時による反応温度の上昇が抑制されるものと考えられる。したがって、触媒中での反応熱による触媒成分の移動や凝集にともなう触媒成分の状態変化に起因する触媒性能の低下が緩やかになり触媒寿命が向上しうる。その結果、優れた選択率で、長期間安定にアルキレンオキシドを製造しうる、アルキレンオキシド製造用触媒が得られうる。 That is, the catalyst of the present invention is a first selected from the group consisting of silver, cesium (Cs), rhenium (Re), and vanadium (V), molybdenum (Mo), tungsten (W), and sulfur (S). A co-promoter and a second promoter selected from the group consisting of copper (Cu), nickel (Ni), iron (Fe), and cobalt (Co) are included as catalyst components. As described above, among the above catalyst components, rhenium provides excellent selectivity, but its catalytic action decreases in a short time. Here, by using a predetermined first co-promoter, the catalytic function of rhenium can be maintained, but the reaction temperature is increased. However, the present inventors have found for the first time that by using a predetermined second co-promoter, the catalytic activity can be improved, the increase in reaction temperature can be suppressed, and thus the catalyst life can be improved. The mechanism by which such an effect is achieved is unknown, but is presumed as follows. The present invention is not limited by the following estimation. That is, it is considered that vanadium, molybdenum, tungsten, or sulfur acts as an auxiliary promoter for rhenium, suppresses a decrease in rhenium catalytic action, and maintains high selectivity. However, the presence of the first co-promoter reduces the catalytic activity and raises the reaction temperature. On the other hand, the presence of copper, nickel, iron, or cobalt maintains the effects of rhenium and the first co-promoter, and at the same time greatly improves the catalytic activity, thus suppressing the increase in reaction temperature over time. It is considered to be done. Therefore, the catalyst performance deterioration due to the change in the state of the catalyst component accompanying the movement or aggregation of the catalyst component due to the heat of reaction in the catalyst is moderated, and the catalyst life can be improved. As a result, an alkylene oxide production catalyst capable of producing alkylene oxide stably for a long period of time with excellent selectivity can be obtained.
以下、本発明の実施の形態を説明する。なお、本発明は、以下の実施の形態のみには限定されない。 Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment.
また、本明細書において、範囲を示す「Ｘ〜Ｙ」は「Ｘ以上Ｙ以下」を意味し、「重量」と「質量」、「重量％」と「質量％」、「重量部」と「質量部」、および「重量ｐｐｍ」と「質量ｐｐｍ」は同義語として扱う。また、特記しない限り、操作および物性等の測定は室温（２０〜２５℃）／相対湿度４０〜５０％の条件で測定する。また、「ｐｐｍ」は、特に断りがない限り、「重量ｐｐｍ」または「質量ｐｐｍ」である。 In the present specification, “X to Y” indicating a range means “X or more and Y or less”, “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Parts by mass” and “weight ppm” and “mass ppm” are treated as synonyms. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%. Further, “ppm” is “weight ppm” or “mass ppm” unless otherwise specified.
（担体）
担体は、α−アルミナを主成分とすること以外は特に制限されない。
(Carrier)
The carrier is not particularly limited except that α-alumina is the main component.
本明細書において、担体が「α−アルミナを主成分とする」とは、担体におけるα−アルミナの含有量が、担体の全質量に対して、９０質量％以上であることを意味する。担体におけるα−アルミナの含有量は、好ましくは９５質量％以上であり、より好ましくは９７質量％以上である。ここで、担体におけるα−アルミナの含有量の上限は、１００質量％である。 In this specification, the carrier “having α-alumina as a main component” means that the content of α-alumina in the carrier is 90% by mass or more based on the total mass of the carrier. The content of α-alumina in the support is preferably 95% by mass or more, more preferably 97% by mass or more. Here, the upper limit of the content of α-alumina in the carrier is 100% by mass.
担体は、α−アルミナを主成分とするものであればその他の組成は特に制限されないが、例えば、アルカリ金属またはアルカリ土類金属の酸化物や遷移金属の酸化物を含有しうる。これらの含有量についても特に制限はないが、アルカリ金属の酸化物（例えば、Ｎａ２Ｏ）またはアルカリ土類金属の酸化物の含有量は、酸化物換算で、担体の全質量に対して、好ましくは０．００１〜５質量％であり、より好ましくは０．０１〜１．０質量％である。Ｎａ２Ｏの含有量は、担体の全質量に対して、好ましくは０．００１〜５．０質量％であり、より好ましくは０．０１〜１．０質量％であり、さらに好ましくは０．１〜０．８質量％であり、特に好ましくは０．１５〜０．５質量％である。Ｎａ２Ｏの含有量が０．００１質量％以上であれば、優れた寿命安定性が得られうる。また、Ｎａ２Ｏの含有量が５．０質量％以下であれば、高い選択性が得られうる。また、担体調製の際に、遷移金属またはその化合物を添加しないことが好ましい。 The support is not particularly limited as long as it has α-alumina as a main component, but may contain, for example, an oxide of an alkali metal or alkaline earth metal or an oxide of a transition metal. These contents are not particularly limited, but the content of an alkali metal oxide (for example, Na 2 O) or an alkaline earth metal oxide is based on the total mass of the support in terms of oxide. Preferably it is 0.001-5 mass%, More preferably, it is 0.01-1.0 mass%. The content of Na 2 O is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.001% by mass with respect to the total mass of the carrier. It is 1-0.8 mass%, Most preferably, it is 0.15-0.5 mass%. When the content of Na 2 O is 0.001% by mass or more, excellent life stability can be obtained. Moreover, if the content of Na 2 O is 5.0% by mass or less, high selectivity can be obtained. Moreover, it is preferable not to add a transition metal or a compound thereof during the preparation of the carrier.
また、本発明に係る担体は、シリカ（酸化ケイ素、ＳｉＯ２）を含有してもよい。ここで、担体におけるシリカの含有量は、特に制限されないが、担体の全質量に対して、好ましくは０．１〜１０質量％であり、より好ましくは０．５〜５質量％であり、さらに好ましくは１．０〜３．０質量％である。担体中のＳｉＯ２の含有量が０．１質量％以上であれば、優れた寿命安定性が得られうる。また、ＳｉＯ２の含有量が１０質量％以下であれば、高い選択性が得られうる。 Further, the carrier according to the present invention may contain silica (silicon oxide, SiO 2 ). Here, the content of silica in the carrier is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, further based on the total mass of the carrier. Preferably it is 1.0-3.0 mass%. If the content of SiO 2 in the support is 0.1% by mass or more, excellent life stability can be obtained. Moreover, if the content of SiO 2 is 10% by mass or less, high selectivity can be obtained.
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ＢＲＵＫＥＲ社製Ｓ８ ＴＩＧＥＲを用い、ファンダメンタルパラメータ法（ＦＰ法）または検量線法にて測定することができる。本明細書において、担体の組成や各成分の含有量は、下記実施例に記載される方法によって測定される値である。 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, S8 TIGER manufactured by BRUKER is used as a measuring device, and measurement can be performed by a fundamental parameter method (FP method) or a calibration curve method. In the present specification, the composition of the carrier and the content of each component are values measured by the methods described in the following examples.
担体の細孔容積は、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に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。ここで、担体の細孔容積は、水銀圧入法により、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。 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, still more preferably 0.3 to 0.00. 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. Here, the pore volume of the carrier is 1.0 to 60 by using Autopore III 9420W (manufactured by Shimadzu Corporation) as a measuring device using a carrier deaerated at 200 ° C. for at least 30 minutes by a mercury intrusion method. A value measured at a pressure range of 000 psia and 60 measurement points is 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５〜１０ｍｍである。なお、担体がリング状である場合の担体のサイズもまた特に制限されないが、例えば、担体の外径（平均直径）は、好ましくは３〜２０ｍｍであり、より好ましくは５〜１０ｍｍである。担体の内径（平均内径）は、好ましくは１〜７ｍｍであり、より好ましくは２〜６ｍｍである。担体の長さ（平均長さ）は、好ましくは３〜２０ｍｍであり、より好ましくは５〜１５ｍｍである。なお、上記担体の外径（平均直径）、内径（平均内径）及び長さ（平均長さ）は、統計学的に有意な平均値（例えば、１００個以上の平均値）でありうる。 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 5-10 mm. In addition, the size of the carrier when the carrier is in a ring shape is also not particularly limited. For example, the outer diameter (average diameter) of the carrier is preferably 3 to 20 mm, and more preferably 5 to 10 mm. The inner diameter (average inner diameter) of the carrier is preferably 1 to 7 mm, more preferably 2 to 6 mm. The length (average length) of the carrier is preferably 3 to 20 mm, more preferably 5 to 15 mm. The outer diameter (average diameter), inner diameter (average inner diameter) and length (average length) of the carrier may be statistically significant average values (for example, an average value of 100 or more).
担体の比表面積もまた、特に制限されないが、担体のＢＥＴ比表面積は、好ましくは０．１〜１０ｍ２／ｇであり、より好ましくは０．１〜５ｍ２／ｇであり、さらに好ましくは０．３〜２ｍ２／ｇであり、特に好ましくは０．６ｍ２／ｇ以上でかつ０．９ｍ２／ｇ未満である。担体のＢＥＴ比表面積が上記範囲であれば、触媒成分を担持するための十分な細孔が確保され、触媒性能に優れる触媒が得られる。また、担体の細孔径がある程度大きい値に維持され、製造された触媒を用いたアルキレンオキシド製造時のアルキレンオキシドの逐次酸化が抑制できる。なお、担体の「ＢＥＴ比表面積（ｍ２／ｇ）」は、物質の比表面積を測定する際に一般的に用いられている装置により求めることができる。本明細書において、担体の「ＢＥＴ比表面積（ｍ２／ｇ）」は、下記実施例に記載される方法によって測定される値である。 The specific surface area of the carrier is also not particularly limited, but the BET specific surface area of the carrier is preferably 0.1 to 10 m 2 / g, more preferably 0.1 to 5 m 2 / g, and still more preferably 0. .3 to 2 m 2 / g, particularly preferably 0.6 m 2 / g or more and less than 0.9 m 2 / g. When the BET specific surface area of the support is in the above range, sufficient pores for supporting the catalyst component are secured, and a catalyst having excellent catalyst performance can be obtained. Further, the pore diameter of the support is maintained at a certain large value, and the sequential oxidation of the alkylene oxide during the production of the alkylene oxide using the produced catalyst can be suppressed. The “BET specific surface area (m 2 / g)” of the carrier can be determined by an apparatus generally used for measuring the specific surface area of the substance. In the present specification, the “BET specific surface area (m 2 / g)” of the carrier is a value measured by the method described in the Examples below.
担体の吸水率は、特に制限されないが、好ましくは１０〜７０％であり、より好ましくは２０〜５０％であり、さらに好ましくは２５〜４５％である。このような吸水率を有する担体は、十分な強度を維持でき、かつ表面積を保持して、触媒成分を担持する際の含浸操作を容易に行うことができる。なお、担体の吸水率の測定方法は、特に制限されず、公知の方法が同様にしてあるいは適宜修飾して適用できる。本明細書において、担体の「吸水率（％）」は、下記実施例に記載される方法によって測定される値である。 Although the water absorption rate of a support | carrier is not restrict | limited in particular, Preferably it is 10-70%, More preferably, it is 20-50%, More preferably, it is 25-45%. The carrier having such a water absorption rate can maintain a sufficient strength, can maintain a surface area, and can easily perform an impregnation operation when supporting a catalyst component. In addition, the measuring method of the water absorption rate of a support | carrier is not restrict | limited in particular, A well-known method can be applied similarly or suitably modified. In the present specification, the “water absorption (%)” of the carrier is a value measured by the method described in the Examples below.
担体の圧壊強度としては、好ましくは４０Ｎ以上であり、より好ましくは５０Ｎ以上であり、さらに好ましくは６０Ｎ以上である。圧壊強度が４０Ｎ以上であれば、反応管への触媒充填の際に触媒の割れや粉化が起こり、圧力損失が大きくなることで装置やユーティリティの面で不利になることを防ぐことができる。担体の圧壊強度の上限値は特に限定されない。なお、担体の圧壊強度の値としては、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。 The crushing strength of the carrier is preferably 40N or more, more preferably 50N or more, and further preferably 60N or more. If the crushing strength is 40 N or more, the catalyst can be prevented from cracking or pulverizing when the catalyst is charged into the reaction tube, and the pressure loss is increased, which is disadvantageous in terms of equipment and utilities. The upper limit value of the crushing strength of the carrier is not particularly limited. In addition, as a value of the crushing strength of the carrier, a value obtained by a method described in Examples described later is adopted.
担体の見かけの気孔率もまた、特に制限されないが、好ましくは４５〜７０％であり、より好ましくは５０〜６０％である。 The apparent porosity of the carrier is also not particularly limited, but is preferably 45 to 70%, more preferably 50 to 60%.
（担体の製造方法）
担体の製造方法は、特に制限されない。例えば、少なくともα−アルミナを主成分とするα−アルミナ粉体と、バインダーと、必要に応じてシリカを提供する原料としてのケイ素化合物と、気孔形成剤と、溶媒と、を混練して杯土を調製し、得られた杯土を適当な形状に成形した後、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焼成する方法が好ましく使用される。
(Method for producing carrier)
The method for producing the carrier is not particularly limited. For example, an α-alumina powder containing at least α-alumina as a main component, a binder, and, if necessary, a silicon compound as a raw material for providing silica, a pore-forming agent, and a solvent, are kneaded to prepare a clay. It is preferable to use a method in which the obtained clay is formed into an appropriate shape, dried if necessary, and fired in an inert gas such as helium, nitrogen and argon and / or a gas atmosphere such as air. Is done.
担体原料のα−アルミナ粉体の純度（含有量）は、９０質量％以上、好ましくは９５質量％以上、更に好ましくは９９質量％以上、特に好ましくは９９．５質量％以上（上限：１００質量％）のものが用いられる。 The purity (content) of the α-alumina powder as the carrier material is 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, and particularly preferably 99.5% by mass or more (upper limit: 100% by mass). %) Is used.
α−アルミナ粉体はほかに、酸化アルミナ、特に無定形のアルミナ、シリカ、シリカアルミナ、ムライトなど（これらを「無定形アルミナ等」と総称する）；酸化カリウム、酸化ナトリウム、酸化セシ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）；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、予めその粉体中の酸化ナトリウム量を把握することにより、担体が所望の酸化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。同様に、所望のシリカ含有量になるように、シリカを提供するためのケイ素化合物を考慮しつつアルミナ源を選定することができる。 In addition, α-alumina powders include alumina oxide, especially amorphous alumina, silica, silica alumina, mullite and the like (collectively referred to as “amorphous alumina etc.”); alkalis such as potassium oxide, sodium oxide, cesium oxide and the like. Metal oxides and alkaline earth metal oxides (these are collectively referred to as “alkalis and the like”). 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 oxide in the powder, a carrier can be obtained by adding a sodium compound at the time of preparing the carrier so that the carrier has a desired sodium oxide content. Similarly, an alumina source can be selected in consideration of a silicon compound for providing silica so as to obtain a desired silica content.
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、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 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, and still more preferably. Is 0.5 to 10 μm, particularly preferably 1 to 5 μm. The secondary particle size 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.
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。 The specific surface area of the α-alumina powder (measured by the BET method using nitrogen gas, hereinafter abbreviated as BET specific surface area) is not particularly limited, but the BET specific surface area of the α-alumina powder is preferably 0. 0.01 to 20 m 2 / g, more preferably 0.1 to 10 m 2 / g, still more preferably 0.1 to 5 m 2 / g, and particularly preferably 0.3 to 4 m 2 / g. is there.
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.
上記ケイ素化合物としては、酸化ケイ素、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。 Examples of the silicon compound include covalently bonded compounds such as silicon oxide, silicon nitride, silicon carbide, silane, and silicon sulfide; such as sodium silicate, ammonium silicate, sodium aluminosilicate, ammonium aluminosilicate, sodium phosphosilicate, and ammonium phosphosilicate. Silicates; 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.
上記バインダーは、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、カルボキシメチルセルロース、コーンスターチまたはそ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 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, carboxymethyl cellulose, corn starch or an alkali metal salt thereof. Among these, it is preferable to use carboxymethylcellulose, sodium carboxymethylcellulose, and the like.
気孔形成剤は、特に制限されないが、添加によって触媒性能に悪影響を及ぼさないものが好ましい。具体的には、コークス、炭素粉末、グラファイト、（ポリアルキレン、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、桃、杏、くるみ等の殻のような他の植物材料等の炭質材料である。炭素基材バインダーもまた気孔形成剤として使用することができる。これらうち、粉砕堅果穀、カシュー、桃、杏、くるみ等の殻のような炭質材料が好ましい。これらの気孔形成剤は、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。また、気孔形成剤の大きさは、特に制限されないが、気孔形成剤の平均粒径（直径）が、５０〜１０００μｍであることが好ましく、１００〜８５０μｍであることがより好ましい。このような所望の粒径を有する気孔形成剤は、所望の目開きを有するメッシュで分級することによって、容易に得られる。気孔形成剤の添加量は、特に制限されないが、α−アルミナ粉体１００質量部に対して、好ましくは１５．５〜４５質量部であり、より好ましくは１７〜３５質量部である。 The pore forming agent is not particularly limited, but is preferably one that does not adversely affect the catalyst performance by addition. Specifically, coke, carbon powder, graphite, powder plastic (such as polyalkylene, polystyrene, polycarbonate, etc.), cellulose and cellulose-based materials, sawdust, and shells of ground nuts, cashews, peaches, apricots, walnuts, etc. It is a carbonaceous material such as other plant material. Carbon substrate binders can also be used as pore formers. Of these, carbonaceous materials such as ground nuts, cashews, peaches, apricots, and walnuts are preferred. These pore formers are completely removed from the support during firing, leaving controlled pores in the support. The size of the pore forming agent is not particularly limited, but the average particle size (diameter) of the pore forming agent is preferably 50 to 1000 μm, and more preferably 100 to 850 μm. A pore forming agent having such a desired particle size can be easily obtained by classification with a mesh having a desired opening. The addition amount of the pore forming agent is not particularly limited, but is preferably 15.5 to 45 parts by mass, more preferably 17 to 35 parts by mass with respect to 100 parts by mass of the α-alumina powder.
混合物を調製するために使用される溶媒は、特に制限されないが、担体製造の生産性、安全性、及びコストなどを考慮すると、水およびメタノール、エタノール、プロパノール、イソプロパノールなどのアルコール類などが挙げられ、特に水が好ましい。 The solvent used for preparing the mixture is not particularly limited, but water and alcohols such as methanol, ethanol, propanol, isopropanol, and the like are considered in consideration of productivity, safety, and cost of carrier production. In particular, water is preferred.
上記で調製された杯土は、ニーダーなどの混練機を用いて十分に混合することが好ましい。このようにして混錬した後は、押し出し成型などにより適当な金型を用いて所望の形状に成型（または造粒）し、乾燥した後、焼成する。これらの調製方法については、例えば、「多孔質体の性質とその応用技術」竹内雍監修、株式会社フジ・テクノシステム発行（１９９９年）に記載されている。また、特開平５−３２９３６８号公報、特開２００１−６２２９１号公報、特開２００２−１３６８６８号公報、特許第２９８３７４０号公報、特許第３２５６２３７号公報、特許第３２９５４３３号公報なども参照されうる。ここで、乾燥条件は、成形物が十分乾燥される条件であれば特に制限されないが、例えば、６０〜１５０℃で１〜１００時間程度で成形物を乾燥することが好ましい。また、焼成条件もまた、特に制限されず、公知の担体の製造条件と同様の条件が適用できる。例えば、上記で乾燥されたものを、ヘリウム、窒素、アルゴン等の不活性ガスおよび空気等のガス雰囲気下で、好ましくは１，０００〜１，８００℃、より好ましくは１，２００〜１，７００℃で、好ましくは１〜１００時間、より好ましくは１〜２０時間程度、焼成する。 It is preferable that the clay prepared as described above is sufficiently mixed using a kneader such as a kneader. After kneading in this way, it is molded (or granulated) into a desired shape using an appropriate mold by extrusion molding or the like, dried, and fired. These preparation methods are described in, for example, “Characteristics of Porous Materials and Their Application Technologies”, supervised by Satoshi Takeuchi, published by Fuji Techno System Co., Ltd. (1999). Reference can also be made to JP-A-5-329368, JP-A-2001-62291, JP-A-2002-136868, JP-A-2984740, JP-A-3256237, JP-A-3295433, and the like. Here, the drying conditions are not particularly limited as long as the molded product is sufficiently dried. For example, it is preferable to dry the molded product at 60 to 150 ° C. for about 1 to 100 hours. Also, the baking conditions are not particularly limited, and the same conditions as known carrier production conditions can be applied. For example, what was dried above is preferably 1,000 to 1,800 ° C., more preferably 1,200 to 1,700 in a gas atmosphere such as an inert gas such as helium, nitrogen and argon and air. The baking is performed at a temperature of preferably 1 to 100 hours, more preferably about 1 to 20 hours.
担体の比表面積は、α−アルミナ粉体の比表面積、バインダー成分、焼成温度等を適宜選択することにより調整することができる。 The specific surface area of the carrier can be adjusted by appropriately selecting the specific surface area of the α-alumina powder, the binder component, the firing temperature, and the like.
また、担体中のシリカ含有量は、α−アルミナ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、これらを勘案し調整すればよい。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から算出することができ、これら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付け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ほうが好ましい。 The silica content in the carrier can be calculated from the amount of silica contained in the α-alumina powder and the silicon compound, and may be adjusted in consideration of these. The sodium content in the carrier can be calculated from the amount of sodium contained in the silicon compound, the organic binder, and α-alumina, and may be adjusted in consideration of these. Furthermore, the content may be adjusted by retrofitting a silicon compound or a compound containing sodium to the carrier containing SiO 2 or Na 2 O thus obtained. It is more preferable to add a sodium compound.
（触媒成分）
本発明の触媒は、α−アルミナを主成分とする担体に、少なくとも、銀、セシウム、レニウム、ならびにバナジウム、モリブデン、タングステン、および硫黄からなる群から選択される第１共促進剤、ならびに銅、ニッケル、鉄、およびコバルトからなる群から選択される第２共促進剤を含む触媒成分が担持されてなる。
(Catalyst component)
The catalyst of the present invention comprises, on a carrier based on α-alumina, at least a first co-promoter selected from the group consisting of silver, cesium, rhenium, and vanadium, molybdenum, tungsten, and sulfur, and copper. A catalyst component containing a second co-promoter selected from the group consisting of nickel, iron, and cobalt is supported.
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、アルキ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、アルキ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）、（銀（Ａｇ）換算）で、好ましくは３０質量％未満であり、より好ましくは１質量％以上３０質量％未満であり、さらにより好ましくは３〜２５質量％であり、特に好ましくは５〜２０質量％である。このような範囲であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキレンオキシドを効率よく製造することができる。 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 alkylene oxide. Further, the silver content (supported amount) is not particularly limited, but is based on the mass of the catalyst for producing an alkylene oxide (based on the total mass of the carrier and the catalyst component; hereinafter the same), (in terms of silver (Ag)) The amount is preferably less than 30% by mass, more preferably 1% by mass or more and less than 30% by mass, still more preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass. Within such a range, alkylene oxide can be efficiently produced by vapor phase oxidation of alkylene with a molecular oxygen-containing gas.
また、セシウム（Ｃｓ）、レニウム（Ｒｅ）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、アルキレンオキシドの製造に有効な量で担持すればよい。 Cesium (Cs) and rhenium (Re) generally act as silver reaction accelerators. These contents (supported amounts) are not particularly limited, and may be supported in an amount effective for the production of alkylene oxide.
セシウムの含有量（担持量）は、特に制限されないが、アルキレンオキシド製造用触媒の質量基準（セシウム（Ｃｓ）換算）で、例えば５００〜５０００質量ｐｐｍであり、好ましくは１０００〜４０００質量ｐｐｍであり、より好ましくは１３００〜３０００質量ｐｐｍである。このような範囲であれば、アルキレン（例えば、エチレン）を分子状酸素含有ガスにより気相酸化してアルキレンオキシドを製造する反応を有効に促進できる。 The content (supported amount) of cesium is not particularly limited, but is, for example, 500 to 5000 ppm by mass, preferably 1000 to 4000 ppm by mass, based on the mass of the alkylene oxide production catalyst (converted to cesium (Cs)). More preferably, it is 1300-3000 mass ppm. Within such a range, the reaction for producing alkylene oxide by vapor-phase oxidation of alkylene (for example, ethylene) with a molecular oxygen-containing gas can be effectively promoted.
また、レニウムの含有量（担持量）は、特に制限されないが、アルキレンオキシド製造用触媒の質量基準（レニウム（Ｒｅ）換算）で、例えば５０〜２０００質量ｐｐｍであり、好ましくは１００〜１０００質量ｐｐｍである。このような範囲であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキ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、触媒の選択率を有効に向上できる。レニウムの含有量が２０００質量ｐｐｍ以下であれば、選択率の向上が得られ、反応温度の上昇を抑制できるため、優れた寿命性能が得られうる。 The rhenium content (supported amount) is not particularly limited, but is, for example, 50 to 2000 ppm by mass, preferably 100 to 1000 ppm by mass, based on the mass of the alkylene oxide production catalyst (in terms of rhenium (Re)). It is. If it is such a range, the reaction which manufactures an alkylene oxide by vapor-phase oxidation of alkylene with molecular oxygen containing gas can be accelerated | stimulated effectively. 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. If the rhenium content is 2000 mass ppm or less, the selectivity can be improved, and the reaction temperature can be prevented from rising, so that excellent life performance can be obtained.
さらに、本発明の触媒は、第１共促進剤として、バナジウム、モリブデン、タングステン、および硫黄からなる群から選択される少なくとも１種を含む。ここで、当該第１共促進剤は、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。当該第１共促進剤は、レニウムの補助促進剤（レニウム共促進剤）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、長期間使用しても高い選択性が維持できる。 Further, the catalyst of the present invention contains at least one selected from the group consisting of vanadium, molybdenum, tungsten, and sulfur as the first co-promoter. Here, the first co-promoter may be used alone or in the form of a mixture of two or more. The first co-promoter acts as a rhenium auxiliary promoter (rhenium co-promoter). Thus, the catalyst components of the present invention can maintain high selectivity even when used for a long period of time by the interaction of the catalyst components.
中でも、第１共促進剤としては、バナジウム、モリブデン、またはタングステンを用いることが好ましい。すなわち、本発明の好ましい実施形態において、本発明の触媒は、バナジウム、モリブデン、およびタングステンから選択される１種以上を含み、硫黄の含有量は、アルキレンオキシド製造用触媒の質量基準で、１０質量ｐｐｍ以下である（下限値：０質量ｐｐｍ）。さらに好ましくは、前記第１共促進剤はモリブデンまたはタングステンであり、特に好ましくは、第１共促進剤は、タングステンである。 Among these, vanadium, molybdenum, or tungsten is preferably used as the first co-promoter. That is, in a preferred embodiment of the present invention, the catalyst of the present invention contains one or more selected from vanadium, molybdenum, and tungsten, and the sulfur content is 10 mass based on the mass of the alkylene oxide production catalyst. It is ppm or less (lower limit: 0 mass ppm). More preferably, the first co-promoter is molybdenum or tungsten, and particularly preferably, the first co-promoter is tungsten.
第１共促進剤の含有量（担持量）は、特に制限されず、アルキレンオキシドの製造に有効な量で担持すればよい。第１共促進剤の含有量（担持量）は、特に制限されないが、アルキレンオキシド製造用触媒の質量基準（各金属換算）で、好ましくは１０〜２０００質量ｐｐｍであり、より好ましくは５０〜１０００質量ｐｐｍである。２種以上の第１共促進剤を用いる場合は、これらの含有量の合計が上記範囲であることが好ましい。このような範囲であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキ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、長期間維持できる。 The content (supported amount) of the first co-promoter is not particularly limited, and may be supported in an amount effective for the production of alkylene oxide. The content (supported amount) of the first co-promoter is not particularly limited, but is preferably 10 to 2000 ppm by mass, more preferably 50 to 1000 on a mass basis (in terms of each metal) of the alkylene oxide production catalyst. Mass ppm. When using 2 or more types of 1st co-promoters, it is preferable that the sum total of these content is the said range. Within such a range, when producing alkylene oxide by vapor phase oxidation of alkylene with a molecular oxygen-containing gas, the effect of rhenium (an effect of improving the selectivity of the catalyst) can be promoted and can be maintained for a long time.
また、本発明の触媒は、第２共促進剤として、銅、ニッケル、鉄、およびコバルトからなる群から選択される少なくとも１種を含む。ここで、当該第２共促進剤は、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。当該第２共促進剤は、レニウムおよび第１共促進剤の効果を維持させると同時に、触媒活性を大幅に向上させるため、経時による反応温度の上昇を抑制しうる。そのため、触媒中での反応熱による触媒成分の移動や凝集に伴う触媒成分の状態変化に起因する触媒性能の低下が緩やかになり、触媒寿命が向上しうる。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、高い選択性を長期間にわたって発揮できる。 Moreover, the catalyst of this invention contains at least 1 sort (s) selected from the group which consists of copper, nickel, iron, and cobalt as a 2nd co-promoter. Here, the second co-promoter may be used alone or in the form of a mixture of two or more. The second co-promoter maintains the effects of rhenium and the first co-promoter, and at the same time greatly improves the catalytic activity, and therefore can suppress an increase in reaction temperature over time. Therefore, the catalyst performance deterioration due to the movement of the catalyst component due to the heat of reaction in the catalyst and the change in state of the catalyst component accompanying the aggregation is moderated, and the catalyst life can be improved. Thus, when each catalyst component interacts, the catalyst of this invention can exhibit high selectivity over a long period of time.
第２共促進剤の含有量（担持量）は、特に制限されず、アルキレンオキシドの製造に有効な量で担持すればよいが、第２共促進剤が銅である場合、銅の含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、好ましくは１００質量ｐｐｍ以上であり、より好ましくは２００質量ｐｐｍ以上であり、さらに好ましくは４００質量ｐｐｍ以上である。銅の含有量が１００質量ｐｐｍ以上であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキレンオキシドを製造する際に、触媒の活性を向上させ、反応温度の上昇を抑制する効果がより高く、触媒寿命を向上させる効果が高い。また、銅の含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、好ましくは１５００質量ｐｐｍ以下であり、より好ましくは１２００質量ｐｐｍ以下であり、さらに好ましくは１０００質量ｐｐｍ以下である。銅の含有量が１５００質量ｐｐｍ以下であれば、銅の添加量に応じた効果が得られうる。また、優れた選択性が維持される。また、各触媒成分が効果的に相互作用することによって、より優れた触媒性能が得られうる。 The content (supported amount) of the second co-promoter is not particularly limited and may be supported in an amount effective for the production of alkylene oxide, but when the second co-promoter is copper, the content of copper ( The supported amount) is preferably 100 mass ppm or more, more preferably 200 mass ppm or more, and further preferably 400 mass ppm or more, based on the mass of the alkylene oxide production catalyst (in metal conversion). If the copper content is 100 mass ppm or more, when producing alkylene oxide by vapor phase oxidation of alkylene with a molecular oxygen-containing gas, the activity of the catalyst is improved and the effect of suppressing an increase in reaction temperature is achieved. Higher and more effective in improving catalyst life. Further, the copper content (supported amount) is preferably 1500 ppm by mass or less, more preferably 1200 ppm by mass or less, and still more preferably 1000 ppm by mass basis (metal conversion) of the catalyst for producing alkylene oxide. ppm or less. When the copper content is 1500 ppm by mass or less, an effect corresponding to the amount of copper added can be obtained. In addition, excellent selectivity is maintained. Further, more excellent catalytic performance can be obtained by the effective interaction of the catalyst components.
第２共促進剤としてニッケルを用いる場合、ニッケルの含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、好ましくは９０質量ｐｐｍ以上であり、より好ましくは１００質量ｐｐｍ以上であり、さらに好ましくは１２０質量ｐｐｍ以上である。ニッケルの含有量が９０質量ｐｐｍ以上であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキレンオキシドを製造する際に、触媒の活性を向上させ、反応温度の上昇を抑制する効果がより高く、触媒寿命を向上させる効果が高い。また、ニッケルの含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、例えば１５００質量ｐｐｍ以下であり、好ましくは１０００質量ｐｐｍ以下であり、より好ましくは６００質量ｐｐｍ以下である。ニッケルの含有量が１５００質量ｐｐｍ以下であれば、ニッケルの添加量に応じた効果が得られうる。また、優れた選択性が維持される。また、各触媒成分が効果的に相互作用することによって、より優れた触媒性能が得られうる。 When nickel is used as the second co-promoter, the nickel content (supported amount) is preferably 90 ppm by mass or more, more preferably 100 ppm by mass, based on the mass of the alkylene oxide production catalyst (in terms of metal). It is above, More preferably, it is 120 mass ppm or more. When the content of nickel is 90 ppm by mass or more, when producing alkylene oxide by vapor phase oxidation of alkylene with a molecular oxygen-containing gas, the activity of the catalyst is improved, and the effect of suppressing an increase in the reaction temperature is achieved. Higher and more effective in improving catalyst life. Further, the nickel content (supported amount) is, for example, 1500 mass ppm or less, preferably 1000 mass ppm or less, more preferably 600 mass ppm or less, based on the mass standard (metal conversion) of the alkylene oxide production catalyst. It is. When the content of nickel is 1500 mass ppm or less, an effect corresponding to the amount of nickel added can be obtained. In addition, excellent selectivity is maintained. Further, more excellent catalytic performance can be obtained by the effective interaction of the catalyst components.
第２共促進剤として鉄を用いる場合、鉄の含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、好ましくは１０質量ｐｐｍ以上であり、より好ましくは５０質量ｐｐｍ以上であり、さらに好ましくは１００質量ｐｐｍ以上である。鉄の含有量が１０質量ｐｐｍ以上であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキレンオキシドを製造する際に、触媒の活性を向上させ、反応温度の上昇を抑制する効果がより高く、触媒寿命を向上させる効果が高い。また、鉄の含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、例えば１０００質量ｐｐｍ以下であり、好ましくは８００質量ｐｐｍ以下であり、より好ましくは６００質量ｐｐｍ以下である。鉄の含有量が１０００質量ｐｐｍ以下であれば、鉄の添加量に応じた効果が得られうる。また、優れた選択性が維持される。 When iron is used as the second co-promoter, the iron content (supported amount) is preferably 10 ppm by mass or more, more preferably 50 ppm by mass, based on the mass of the alkylene oxide production catalyst (in terms of metal). It is above, More preferably, it is 100 mass ppm or more. If the iron content is 10 ppm by mass or more, when producing alkylene oxide by vapor-phase oxidation of alkylene with a molecular oxygen-containing gas, the activity of the catalyst is improved and the effect of suppressing an increase in the reaction temperature is achieved. Higher and more effective in improving catalyst life. Further, the iron content (supported amount) is, for example, 1000 mass ppm or less, preferably 800 mass ppm or less, more preferably 600 mass ppm or less, based on the mass standard (metal conversion) of the alkylene oxide production catalyst. It is. When the iron content is 1000 mass ppm or less, an effect corresponding to the amount of iron added can be obtained. In addition, excellent selectivity is maintained.
第２共促進剤としてコバルトを用いる場合、コバルトの含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、好ましくは１６０質量ｐｐｍ以上であり、より好ましくは１８０質量ｐｐｍ以上であり、さらに好ましくは２００質量ｐｐｍ以上である。コバルトの含有量が１６０質量ｐｐｍ以上であれば、アルキレンを分子状酸素含有ガスにより気相酸化してアルキレンオキシドを製造する際に、触媒の活性を向上させ、反応温度の上昇を抑制する効果がより高く、触媒寿命を向上させる効果が高い。また、コバルトの含有量（担持量）は、アルキレンオキシド製造用触媒の質量基準（金属換算）で、好ましくは１５００質量ｐｐｍ以下であり、より好ましくは１０００質量ｐｐｍ以下であり、さらに好ましくは６００質量ｐｐｍ以下である。コバルトの含有量が１５００質量ｐｐｍ以下であれば、コバルトの添加量に応じた効果が得られうる。また、優れた選択性が維持される。 When cobalt is used as the second co-promoter, the cobalt content (supported amount) is preferably 160 ppm by mass or more, more preferably 180 ppm by mass, based on the mass of the alkylene oxide production catalyst (as metal). It is above, More preferably, it is 200 mass ppm or more. If the cobalt content is 160 mass ppm or more, when producing alkylene oxide by vapor phase oxidation of alkylene with a molecular oxygen-containing gas, the activity of the catalyst is improved and the effect of suppressing an increase in the reaction temperature is suppressed. Higher and more effective in improving catalyst life. Further, the content (supported amount) of cobalt is preferably 1500 ppm by mass or less, more preferably 1000 ppm by mass or less, and still more preferably 600 ppm by mass basis (metal conversion) of the catalyst for alkylene oxide production. ppm or less. When the cobalt content is 1500 ppm by mass or less, an effect corresponding to the addition amount of cobalt can be obtained. In addition, excellent selectivity is maintained.
中でも、第２共促進剤としては、鉄、ニッケル、または銅を用いることが好ましい。すなわち、本発明の好ましい実施形態において、本発明の触媒は、鉄、ニッケル、および銅から選択される１種以上を含み、コバルトの含有量は、アルキレンオキシド製造用触媒の質量基準で、８質量ｐｐｍ以下、特には５質量ｐｐｍ以下である（下限値：０質量ｐｐｍ）。さらに好ましくは、第２共促進剤は銅またはニッケルであり、特に好ましくは銅である。 Among these, it is preferable to use iron, nickel, or copper as the second co-promoter. That is, in a preferred embodiment of the present invention, the catalyst of the present invention contains one or more selected from iron, nickel, and copper, and the cobalt content is 8 mass based on the mass of the catalyst for producing alkylene oxide. ppm or less, particularly 5 mass ppm or less (lower limit: 0 mass ppm). More preferably, the second co-promoter is copper or nickel, particularly preferably copper.
なお、２種以上の第２共促進剤を用いる場合は、少なくとも１種の第２共促進剤の含有量が上記の範囲であることが好ましく、すべての第２共促進剤の含有量がそれぞれ上記の範囲であることがより好ましい。 In addition, when using 2 or more types of 2nd co-promoters, it is preferable that content of at least 1 type of 2nd co-promoter is said range, and content of all the 2nd co-promoters is respectively It is more preferable to be in the above range.
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、クロム、マンガン、ニオブ、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、好ましくはアルキレンオキシド製造用触媒の質量基準（各金属換算）で、１０〜１０００質量ｐｐｍである。 In addition to the catalyst component, other catalyst components may be included. Here, the other catalyst components are not particularly limited, and examples thereof include chromium, manganese, niobium, tin, antimony, tantalum, bismuth, titanium, and zirconium. In addition, the content (supported amount) of such other catalyst components is not particularly limited as long as the effect of the catalyst component according to the present invention is not impaired, but is preferably based on the mass standard (in terms of each metal) of the alkylene oxide production catalyst. 10 to 1000 ppm by mass.
なお上述した触媒の組成や各成分の含有量（担持量）は、後述の実施例のように触媒前駆体溶液における、各成分の前駆体の使用量から計算して求めることができるが、例えば、蛍光Ｘ線分析法を用いて測定できる。より具体的には、測定装置としてＢＲＵＫＥＲ社製Ｓ８ ＴＩＧＥＲ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。蛍光Ｘ線分析法であれば、触媒および担体の成分を算出し、差分から求めることができる。または、担持された触媒成分を抽出し分析することで確認することができる。また、触媒前駆体溶液の調製、含浸の際に使用した器具に付着した成分量からも算出できる。 The composition of the catalyst and the content (supported amount) of each component described above can be obtained by calculating from the usage amount of the precursor of each component in the catalyst precursor solution as in the examples described later. , And can be measured using fluorescent X-ray analysis. More specifically, it can be measured by the fundamental parameter method (FP method) or the calibration curve method using S8 TIGER manufactured by BRUKER as a measuring device. If it is a fluorescent X ray analysis method, the component of a catalyst and a support | carrier can be calculated and it can obtain | require from a difference. Alternatively, it can be confirmed by extracting and analyzing the supported catalyst component. It can also be calculated from the amount of components adhering to the instrument used during the preparation and impregnation of the catalyst precursor solution.
（アルキレンオキシド製造用触媒の製造方法）
本発明のアルキレンオキシド製造用触媒は、例えば、上記したような担体を使用して、従来公知のアルキ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、本発明のアルキレンオキシド製造用触媒の製造方法の好ましい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。
(Method for producing catalyst for producing alkylene oxide)
The alkylene oxide production catalyst of the present invention can be prepared, for example, according to a conventionally known method for producing an alkylene oxide production catalyst, using the above-described support. Hereinafter, preferred embodiments of the method for producing an alkylene oxide production catalyst of 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、銀の前駆体としては、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。また、レニウムの前駆体としては、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。セシウムの前駆体としては、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、モリブデン酸塩などが挙げられる。これらのうち、硝酸セシウム、過レニウム酸セシウム、モリブデン酸セシウムが好ましい。 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 in a form that dissolves in a solvent. For example, as a precursor of silver, silver nitrate, silver carbonate, silver oxalate, silver acetate, silver propionate, Examples include silver lactate, silver citrate, and silver neodecanoate. Of these, silver oxalate and silver nitrate are preferred. Examples of rhenium precursors include ammonium perrhenate, sodium perrhenate, potassium perrhenate, perrhenic acid, rhenium chloride, rhenium oxide, and cesium perrhenate. Of these, ammonium perrhenate and cesium perrhenate are preferred. Examples of the cesium precursor include cesium nitrate, nitrite, carbonate, oxalate, halide, acetate, sulfate, perrhenate, and molybdate. Of these, cesium nitrate, cesium perrhenate, and cesium molybdate are preferable.
また、第１共促進剤としてモリブデンを用いる場合には、モリブデンの前駆体として、酸化モリブデン、モリブデン酸、モリブデン酸塩、その他、ケイモリブデン酸、リンモリブデ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、パラモリブデン酸アンモニウム、パラモリブデン酸セシウム、リンモリブデン酸アンモニウム、リンモリブデン酸セシウム、ケイモリブデン酸アンモニウム、ケイモリブデン酸セシウムが好ましい。 When molybdenum is used as the first co-promoter, the precursor of molybdenum is molybdenum oxide, molybdic acid, molybdate, heteropolyacids such as silicomolybdic acid, phosphomolybdic acid, and / or heteropolyacid. Examples include salt. Of these, ammonium paramolybdate, cesium paramolybdate, ammonium phosphomolybdate, cesium phosphomolybdate, ammonium silicomolybdate, and cesium silicomolybdate are preferred.
タングステンの場合には、タングステンの前駆体として、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。 In the case of tungsten, examples of the precursor of tungsten include heteropolyacids such as tungsten oxide, tungstic acid, tungstate, phosphotungstic acid, and silicotungstic acid, and / or salts of heteropolyacid. Of these, ammonium metatungstate, cesium metatungstate, ammonium paratungstate, cesium paratungstate, ammonium phosphotungstate, cesium phosphotungstate, ammonium silicotungstate, and cesium silicotungstate are preferred.
バナジウムの場合には、バナジウムの前駆体として、酸化バナジウム、バナジン酸、バナジン酸塩などが挙げられる。これらのうち、メタバナジン酸アンモニウム、メタバナジン酸セシウム、オルトバナジン酸アンモニウム、オルトバナジン酸セシウムが好ましい。 In the case of vanadium, examples of vanadium precursors include vanadium oxide, vanadic acid, and vanadate. Of these, ammonium metavanadate, cesium metavanadate, ammonium orthovanadate, and cesium orthovanadate are preferred.
硫黄の場合には、硫黄の前駆体として、任意の硫酸塩、亜硫酸塩、重亜硫酸塩、スルホン酸塩、過硫酸塩、チオ硫酸塩、ジチオン酸塩などが挙げられる。これらのうち、硫酸セシウムなどのアルカリ金属硫酸塩や、硫酸アンモニウムが好ましい。 In the case of sulfur, examples of the sulfur precursor include arbitrary sulfates, sulfites, bisulfites, sulfonates, persulfates, thiosulfates, and dithionates. Of these, alkali metal sulfates such as cesium sulfate and ammonium sulfate are preferable.
第２共促進剤である銅の前駆体としては、例えば、酸化銅（Ｉ）、酸化銅（ＩＩ）、硝酸銅（Ｉ）、硝酸銅（ＩＩ）、亜硝酸銅（Ｉ）、亜硝酸銅（ＩＩ）、硫酸銅（Ｉ）、硫酸銅（ＩＩ）、亜硫酸銅（Ｉ）、亜硫酸銅（ＩＩ）、酢酸銅（ＩＩ）、クエン酸銅（ＩＩ）、シュウ酸銅（ＩＩ）、塩化銅（Ｉ）などが挙げられる。これらのうち、硝酸銅、硫酸銅が好ましい。 Examples of the precursor of copper that is the second co-promoter include copper oxide (I), copper oxide (II), copper nitrate (I), copper nitrate (II), copper nitrite (I), and copper nitrite. (II), copper sulfate (I), copper sulfate (II), copper sulfite (I), copper sulfite (II), copper acetate (II), copper citrate (II), copper oxalate (II), copper chloride (I) etc. are mentioned. Of these, copper nitrate and copper sulfate are preferred.
ニッケルの前駆体としては、例えば、酸化ニッケル（ＩＩ）、酸化ニッケル（ＩＩＩ）、硝酸ニッケル（ＩＩ）、亜硝酸ニッケル、硫酸ニッケル、亜硫酸ニッケル、酢酸ニッケル、クエン酸ニッケル、乳酸ニッケル、シュウ酸ニッケル、塩化ニッケル、炭酸ニッケルなどが挙げられる。これらのうち、硝酸ニッケル、硫酸ニッケル、炭酸ニッケルが好ましい。 Examples of the nickel precursor include nickel (II) oxide, nickel (III) oxide, nickel (II) nitrate, nickel nitrite, nickel sulfate, nickel sulfite, nickel acetate, nickel citrate, nickel lactate, nickel oxalate , Nickel chloride, nickel carbonate and the like. Of these, nickel nitrate, nickel sulfate, and nickel carbonate are preferred.
コバルトの前駆体としては、例えば、酸化コバルト（ＩＩ）、硝酸コバルト（ＩＩ）、硝酸コバルト（ＩＩＩ）、亜硝酸コバルト（ＩＩ）、硫酸コバルト（ＩＩ）、硫酸コバルト（ＩＩＩ）、酢酸コバルト（ＩＩ）、酢酸コバルト（ＩＩＩ）、クエン酸コバルト（ＩＩ）、クエン酸コバルト（ＩＩＩ）、乳酸コバルト（ＩＩ）、乳酸コバルト（ＩＩＩ）、シュウ酸コバルト（ＩＩ）、シュウ酸コバルト（ＩＩＩ）、塩化コバルト（ＩＩ）、塩化コバルト（ＩＩ）などが挙げられる。これらのうち、硝酸コバルト、硫酸コバルトが好ましい。 Examples of the cobalt precursor include cobalt oxide (II), cobalt nitrate (II), cobalt nitrate (III), cobalt nitrite (II), cobalt sulfate (II), cobalt sulfate (III), and cobalt acetate (II). ), Cobalt (III) acetate, cobalt (II) citrate, cobalt (III) citrate, cobalt (II) lactate, cobalt (III) lactate, cobalt (II) oxalate, cobalt (III) oxalate, cobalt chloride (II), cobalt (II) chloride, etc. are mentioned. Of these, cobalt nitrate and cobalt sulfate are preferred.
鉄の前駆体としては、例えば、酸化鉄（ＩＩ）、酸化鉄（ＩＩＩ）、硝酸鉄（ＩＩ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸鉄（ＩＩＩ）、酢酸鉄（ＩＩ）、酢酸鉄（ＩＩＩ）、クエン酸鉄（ＩＩ）、クエン酸鉄（ＩＩＩ）、乳酸鉄（ＩＩ）、乳酸鉄（ＩＩＩ）、シュウ酸鉄（ＩＩ）、シュウ酸鉄（ＩＩＩ）、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）などが挙げられる。これらのうち、硝酸鉄、硫酸鉄が好ましい。 Examples of iron precursors include iron oxide (II), iron oxide (III), iron nitrate (II), iron nitrate (III), iron sulfate (II), iron sulfate (III), and iron acetate (II). , Iron (III) acetate, iron (II) citrate, iron (III) citrate, iron (II) lactate, iron (III) lactate, iron (II) oxalate, iron (III) oxalate, iron chloride ( II), iron (III) chloride and the like. Of these, iron nitrate and iron sulfate are preferred.
上記各触媒成分の前駆体は、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、上記各触媒成分の前駆体の添加量は、上記した所定の触媒組成となるように適宜決定できる。すなわち、上記した銀、セシウム、レニウム、第１共促進剤、および第２共促進剤の含有量（担持量）となるように、銀、セシウム、レニウム、第１共促進剤、および第２共促進剤のそれぞれの前駆体の添加量を選択すればよい。 The precursors 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 the precursor of each said catalyst component can be suitably determined so that it may become the above-mentioned predetermined catalyst composition. That is, silver, cesium, rhenium, the first co-promoter, and the second co-promoter so that the content (supported amount) of the above-described silver, cesium, rhenium, the first co-promoter, and the second co-promoter is obtained. What is necessary is just to select the addition amount of each precursor of a promoter.
上記各触媒成分の前駆体を溶解する溶媒もまた、各触媒成分の前駆体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、ならびにトルエンなど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 the precursor of each catalyst component. Specific examples include water, alcohols such as methanol and ethanol, and aromatic compounds such as 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、ピリジン、ブチルアミン、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、ブチレンジアミンなどが挙げられる。上記錯化剤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。錯化剤の添加量は、特に制限されないが、例えば、銀化合物と錯化剤とが錯体を形成するように、銀化合物と等モル量となるようにするのがよい。このように銀化合物と錯化剤との錯体を生成させることにより、含浸液は溶液状となり含浸作業が容易となる。 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 pyridine, butylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, and butylenediamine. The complexing agent may be used alone or in the form of a mixture of two or more. The addition amount of the complexing agent is not particularly limited. For example, the complexing agent may be equimolar with the silver compound so that the silver compound and the complexing agent form a complex. By thus forming a complex of the silver compound and the complexing agent, the impregnation liquid becomes a solution and the impregnation operation is facilitated.
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。含浸工程は２０〜１２０℃の温度で０．１〜１０時間行うことが好ましい。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. The impregnation step is preferably performed at a temperature of 20 to 120 ° C. for 0.1 to 10 hours. 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１５０〜７００℃の温度で０．１〜１００時間、好ましくは０．２〜１０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。好ましくは、２段階以上の焼成を行う。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１００〜３００℃にて０．１〜１０時間行った後、２段階目の焼成を空気雰囲気中で３００℃を超えて４５０℃にて０．１〜１０時間行う条件が挙げられる。別の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１００〜３００℃にて０．１〜１０時間行った後、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３００℃を超えて８００℃以下、より好ましくは４００〜７００℃にて、０．１〜１０時間、より好ましくは１〜５時間、焼成を行う。このような条件で行うことによって、触媒寿命をより向上することができる。 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 150 to 700 ° C. for 0.1 to 100 hours, preferably 0. .2 to about 10 hours. In addition, baking may be performed only in one step or may be performed in two or more steps. Preferably, two or more stages of baking are performed. As preferable firing conditions, the first stage firing is performed at 100 to 300 ° C. for 0.1 to 10 hours in an air atmosphere, and then the second stage firing is performed at 300 ° C. to 450 ° C. in the air atmosphere. Conditions for 0.1 to 10 hours. As another preferable firing condition, the first stage firing is performed in an air atmosphere at 100 to 300 ° C. for 0.1 to 10 hours, and then in an inert gas (for example, nitrogen, helium, argon, etc.) atmosphere. The baking is performed at a temperature exceeding 300 ° C. and not more than 800 ° C., more preferably 400 to 700 ° C., for 0.1 to 10 hours, more preferably 1 to 5 hours. By carrying out under such conditions, the catalyst life can be further improved.
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、本発明のアルキレンオキシド製造用触媒を使用することによって、アルキレンオキシド、特に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 alkylene oxide of the present invention, alkylene oxide, particularly ethylene oxide can be produced with high selectivity over a long period of time, which is very useful in industry.
（アルキレンオキシドの製造方法）
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アルキレン（特にエチレン）を気相酸化するアルキレンオキシド、特にエチレンオキシドの製造方法もまた提供される。すなわち、本発明の触媒の存在下で、炭素数２〜２０の不飽和炭化水素を分子状酸素含有ガスにより気相酸化することを有する、アルキレンオキシドの製造方法をも提供される。
(Method for producing alkylene oxide)
The present invention also provides a process for producing alkylene oxide, particularly ethylene oxide, in which alkylene (especially ethylene) is vapor-phase oxidized using a molecular oxygen-containing gas in the presence of the catalyst of the present invention. That is, there is also provided a method for producing an alkylene oxide, which comprises gas phase oxidation of an unsaturated hydrocarbon having 2 to 20 carbon atoms with a molecular oxygen-containing gas in the presence of the catalyst of the present invention.
本発明の方法は、特にエチレンオキシドまたは３，４−エポキシ−１−ブテンの製造に好適に使用できる。このため、不飽和炭化水素がエチレンでありかつアルキレンオキシドがエチレンオキシドである、または不飽和炭化水素が１，３−ブタジエンでありかつアルキレンオキシドが３，４−エポキシ−１−ブテンであることが好ましい。 The method of the present invention can be suitably used particularly for the production of ethylene oxide or 3,4-epoxy-1-butene. For this reason, it is preferable that the unsaturated hydrocarbon is ethylene and the alkylene oxide is ethylene oxide, or the unsaturated hydrocarbon is 1,3-butadiene and the alkylene oxide is 3,4-epoxy-1-butene. .
アルキレンオキシドの製造方法は、触媒として本発明のアルキ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。 The method for producing alkylene oxide can be carried out according to a conventional method except that the catalyst for producing alkylene oxide of the present invention is used as a catalyst.
以下、エチレンオキシドの製造方法の好ましい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の触媒を使用することによって、アルキレンオキシド（エチレンオキシドを含む）を製造できる。 Hereinafter, preferred embodiments of the method for producing ethylene oxide will be described. However, the present invention is not limited to the following preferred embodiments, and alkylene oxides (including ethylene oxide) can be produced by appropriately modifying or using the catalyst of the present invention in other known methods.
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０．２〜４ＭＰａ、好ましくは０．５〜３ＭＰａ、空間速度１，０００〜３０，０００ｈｒ−１（ＳＴＰ）、好ましくは３，０００〜８，０００ｈｒ−１（ＳＴＰ）が採用される。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塩化アルキルを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。 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 MPa, preferably 0.5 to 3 MPa, and a space velocity of 1,000 to 30. , 000 hr −1 (STP), preferably 3,000 to 8,000 hr −1 (STP) is employed. 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 alkyl chloride such as ethyl chloride, ethylene dichloride, vinyl chloride and methyl chloride as reaction inhibitors. 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。下記実施例において、特記しない限り、操作は室温（２５℃）で行われた。また、特記しない限り、「％」および「部」は、それぞれ、「質量％」および「質量部」を意味する。 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. In the following examples, the operations were performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.
また、担体の組成、比表面積、吸水率、細孔容積、圧壊強度は、下記方法によって測定した。 The composition, specific surface area, water absorption, pore volume, and crushing strength of the support were measured by the following methods.
（担体の組成）
担体の組成は、下記方法によって測定する。
(Composition of carrier)
The composition of the carrier is measured by the following method.
粉砕した担体を、直径約３ｃｍのディスク状にプレスした後、ＢＲＵＫＥＲ社製Ｓ８ ＴＩＧＥＲにてＦＰ法或いは必要に応じて検量線法にて測定する。 The crushed carrier is pressed into a disk shape having a diameter of about 3 cm, and then measured by an FP method or a calibration curve method as necessary with an S8 TIGER manufactured by BRUKER.
（担体の比表面積の測定）
担体の比表面積（ＢＥＴ比表面積）は、下記方法に従って測定する。
(Measurement of specific surface area of carrier)
The specific surface area (BET specific surface area) of the carrier is measured according to the following method.
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）法により測定する。 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 is deaerated at 200 ° C. for at least 30 minutes and measured by the BET (Brunauer-Emmet-Teller) method.
（担体の吸水率の測定）
担体の吸水率は、日本工業規格（ＪＩＳ Ｒ ２２０５（１９９８））に記載の方法に準拠して、以下のａ）〜ｄ）の手法により測定する。
(Measurement of water absorption rate of carrier)
The water absorption rate of the carrier is measured by the following methods a) to d) based on the method described in Japanese Industrial Standard (JIS R 2205 (1998)).
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する（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、飽水サンプルとする；
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））；および
ｄ）上記で得られたＷ１（ｇ）およびＷ２（ｇ）を用い、下記数式１に従って、吸水率（％）を算出する。
a) The carrier is placed in a dryer kept at 120 ° C., and the mass when the constant weight is reached is measured (dry mass: W1 (g));
b) The carrier weighed in a) above is 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 b) above was taken out of the water, quickly wiped with a compress, weighed after removing water droplets (saturated sample mass: W2 (g)); and d) obtained above Using W1 (g) and W2 (g), the water absorption (%) is calculated according to the following formula 1.
（担体の細孔容積の測定）
担体の細孔容積は、下記水銀圧入法に従って測定する。具体的には、２００℃にて少なくとも３０分脱気した担体をサンプルとして使用する。さらに、このようにして得られたサンプルについて、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の圧力範囲および６０個の測定ポイントで細孔分布、細孔容積を得る。
(Measurement of pore volume of support)
The pore volume of the carrier is measured according to the mercury intrusion method described below. Specifically, a carrier deaerated at 200 ° C. for at least 30 minutes is used as a sample. Further, for the sample obtained in this way, using Autopore III9420W (manufactured by Shimadzu Corporation) as a measuring device, pore distribution and pores at a pressure range of 1.0 to 60,000 psia and 60 measurement points. Get volume.
（担体の圧壊強度）
精密力量測定器（丸菱科学機械製作所製）を用いて担体の横方向（長さに対して垂直方向）の圧壊強度を測定し、５０個の平均値を圧壊強度とした。
(Crushing strength of carrier)
The crushing strength in the lateral direction (perpendicular to the length) of the carrier was measured using a precision force meter (manufactured by Maruhishi Kagaku Kikai Seisakusho), and the average value of 50 pieces was taken as the crushing strength.
実施例１
シュウ酸銀２０．０ｇを含む水スラリー（水スラリー中の水の含有量：５ｇ）、硝酸セシウム０．１９２ｇ、過レニウム酸アンモニウム０．０４１ｇ、メタタングステン酸アンモニウム０．０３１ｇ、硝酸銅（ＩＩ）三水和物０．１６０ｇを、約１０ｍＬの水に溶解し、さらに錯化剤としてエチレンジアミン７ｍＬを加え、触媒前駆体溶液を調製した。
Example 1
Water slurry containing 20.0 g of silver oxalate (content of water in water slurry: 5 g), 0.192 g of cesium nitrate, 0.041 g of ammonium perrhenate, 0.031 g of ammonium metatungstate, copper (II) nitrate 0.160 g of trihydrate was dissolved in about 10 mL of water, and further 7 mL of ethylenediamine was added as a complexing agent to prepare a catalyst precursor solution.
この触媒前駆体溶液を、担体ａ（α−アルミナ担体、ＢＥＴ比表面積＝０．６５ｍ２／ｇ、ＳｉＯ２含有量＝２．０質量％、Ｎａ２Ｏ含有量＝０．３５質量％、吸水率＝３９．５％、細孔容積＝０．４５ｍｌ／ｇ、圧壊強度＝１３０Ｎ）５０．０ｇに０．５時間含浸した後、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６００℃で３時間熱処理して触媒Ａを得た。 This catalyst precursor solution was mixed with carrier a (α-alumina carrier, BET specific surface area = 0.65 m 2 / g, SiO 2 content = 2.0 mass%, Na 2 O content = 0.35 mass%, water absorption After impregnating 50.0 g (rate = 39.5%, pore volume = 0.45 ml / g, crushing strength = 130 N) for 0.5 hour, 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 600 ° 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）＝１４．６質量％、Ｃｓ（Ｃｓ換算）＝２１８９質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７７質量ｐｐｍ、Ｗ（Ｗ換算）＝３７０質量ｐｐｍ、Ｃｕ（Ｃｕ質量）＝６９８質量ｐｐｍであった。 The content of each component of the catalyst A thus prepared (mass basis of catalyst) is: Ag (silver equivalent) = 14.6% by mass, Cs (Cs equivalent) = 2189 mass ppm, Re (Re equivalent) = 477 mass ppm, W (W conversion) = 370 mass ppm, Cu (Cu mass) = 698 mass ppm.
実施例２
実施例１において、硝酸銅（ＩＩ）三水和物の添加量を０．０４０ｇとしたこと以外は、実施例１と同様にして、触媒Ｂを得た。
Example 2
In Example 1, Catalyst B was obtained in the same manner as in Example 1, except that the amount of copper (II) nitrate trihydrate added was 0.040 g.
触媒Ｂの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．９質量％、Ｃｓ（Ｃｓ換算）＝２１８４質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７６質量ｐｐｍ、Ｗ（Ｗ換算）＝３６９質量ｐｐｍ、Ｃｕ（Ｃｕ換算）＝１７４質量ｐｐｍであった。 The content of each component of the catalyst B (based on the mass of the catalyst) is as follows: Ag (silver conversion) = 14.9 mass%, Cs (Cs conversion) = 2184 mass ppm, Re (Re conversion) = 476 mass ppm, W ( W conversion) = 369 mass ppm and Cu (Cu conversion) = 174 mass ppm.
実施例３
実施例１において、硝酸銅（ＩＩ）三水和物の添加量を０．３２１ｇとしたこと以外は、実施例１と同様にして、触媒Ｃを得た。
Example 3
In Example 1, Catalyst C was obtained in the same manner as in Example 1 except that the addition amount of copper (II) nitrate trihydrate was 0.321 g.
触媒Ｃの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．５質量％、Ｃｓ（Ｃｓ換算）＝２１９１質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７８質量ｐｐｍ、Ｗ（Ｗ換算）＝３７０質量ｐｐｍ、Ｃｕ（Ｃｕ換算）＝１３９７質量ｐｐｍであった。 The content of each component of catalyst C (catalyst mass standard) is: Ag (silver conversion) = 14.5 mass%, Cs (Cs conversion) = 2191 mass ppm, Re (Re conversion) = 478 mass ppm, W ( W conversion) = 370 mass ppm, Cu (Cu conversion) = 1397 mass ppm.
実施例４
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸ニッケル（ＩＩ）六水和物０．０６４ｇとしたこと以外は、実施例１と同様にして、触媒Ｄを得た。
Example 4
In Example 1, Catalyst D was obtained in the same manner as in Example 1 except that 0.064 g of nickel (II) nitrate hexahydrate was used instead of copper (II) nitrate trihydrate.
触媒Ｄの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．９質量％、Ｃｓ（Ｃｓ換算）＝２１８４質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７６質量ｐｐｍ、Ｗ（Ｗ換算）＝３６９質量ｐｐｍ、Ｎｉ（Ｎｉ換算）＝２１４質量ｐｐｍであった。 The content of each component of the catalyst D (mass basis of the catalyst) is: Ag (silver conversion) = 14.9 mass%, Cs (Cs conversion) = 2184 mass ppm, Re (Re conversion) = 476 mass ppm, W ( W conversion) = 369 mass ppm and Ni (Ni conversion) = 214 mass ppm.
実施例５
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸ニッケル（ＩＩ）六水和物０．０２９ｇを添加したこと以外は、実施例１と同様にして、触媒Ｅを得た。
Example 5
In Example 1, Catalyst E was obtained in the same manner as in Example 1 except that 0.029 g of nickel (II) nitrate hexahydrate was added instead of copper (II) nitrate trihydrate. .
触媒Ｅの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１５．０質量％、Ｃｓ（Ｃｓ換算）＝２１８２質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７５質量ｐｐｍ、Ｗ（Ｗ換算）＝３６９質量ｐｐｍ、Ｎｉ（Ｎｉ換算）＝９６質量ｐｐｍであった。 The content of each component of catalyst E (mass basis of catalyst) is: Ag (silver equivalent) = 15.0 mass%, Cs (Cs equivalent) = 2182 mass ppm, Re (Re equivalent) = 475 mass ppm, W ( W conversion) = 369 mass ppm and Ni (Ni conversion) = 96 mass ppm.
実施例６
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸ニッケル（ＩＩ）六水和物０．３５０ｇを添加したこと以外は、実施例１と同様にして、触媒Ｆを得た。
Example 6
In Example 1, Catalyst F was obtained in the same manner as in Example 1 except that 0.350 g of nickel (II) nitrate hexahydrate was added instead of copper (II) nitrate trihydrate. .
触媒Ｆの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．４質量％、Ｃｓ（Ｃｓ換算）＝２１９３質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７８質量ｐｐｍ、Ｗ（Ｗ換算）＝３７１質量ｐｐｍ、Ｎｉ（Ｎｉ換算）＝１１８４質量ｐｐｍであった。 The content of each component of the catalyst F (mass basis of the catalyst) is: Ag (silver conversion) = 14.4 mass%, Cs (Cs conversion) = 2193 mass ppm, Re (Re conversion) = 478 mass ppm, W ( W conversion) = 371 mass ppm and Ni (Ni conversion) = 1184 mass ppm.
実施例７
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸鉄（ＩＩＩ）九水和物０．１３４ｇを添加したこと以外は、実施例１と同様にして、触媒Ｇを得た。
Example 7
In Example 1, Catalyst G was obtained in the same manner as in Example 1 except that 0.134 g of iron (III) nitrate nonahydrate was added instead of copper (II) nitrate trihydrate. .
触媒Ｇの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．３質量％、Ｃｓ（Ｃｓ換算）＝２１９５質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７８質量ｐｐｍ、Ｗ（Ｗ換算）＝３７１質量ｐｐｍ、Ｆｅ（Ｆｅ換算）＝３０７質量ｐｐｍであった。 The content of each component of the catalyst G (based on the mass of the catalyst) is Ag (silver conversion) = 14.3 mass%, Cs (Cs conversion) = 2195 mass ppm, Re (Re conversion) = 478 mass ppm, W ( W conversion) = 371 mass ppm, Fe (Fe conversion) = 307 mass ppm.
実施例８
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸コバルト０．１２０ｇを添加したこと以外は、実施例１と同様にして、触媒Ｈを得た。
Example 8
In Example 1, Catalyst H was obtained in the same manner as in Example 1 except that 0.120 g of cobalt nitrate was added instead of copper (II) nitrate trihydrate.
触媒Ｈの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．６質量％、Ｃｓ（Ｃｓ換算）＝２１８９質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７７質量ｐｐｍ、Ｗ（Ｗ換算）＝３７０質量ｐｐｍ、Ｃｏ（Ｃｏ換算）＝３９９質量ｐｐｍであった。 The content of each component of the catalyst H (catalyst mass basis) is: Ag (silver equivalent) = 14.6 mass%, Cs (Cs equivalent) = 2189 mass ppm, Re (Re equivalent) = 477 mass ppm, W ( W conversion) = 370 mass ppm and Co (Co conversion) = 399 mass ppm.
実施例９
実施例１において、硝酸銅（ＩＩ）三水和物の添加量を０．１０７ｇとし、さらに、硝酸ニッケル（ＩＩ）六水和物０．０６４ｇを添加したこと以外は、実施例１と同様にして、触媒Ｉを得た。
Example 9
In Example 1, the addition amount of copper (II) nitrate trihydrate was set to 0.107 g, and 0.064 g of nickel (II) nitrate hexahydrate was further added. Thus, catalyst I was obtained.
触媒Ｉの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．７質量％、Ｃｓ（Ｃｓ換算）＝２１８７質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７７質量ｐｐｍ、Ｗ（Ｗ換算）＝３７０質量ｐｐｍ、Ｃｕ（Ｃｕ換算）＝４６５質量ｐｐｍ、Ｎｉ（Ｎｉ換算）＝２１５質量ｐｐｍであった。 The content of each component of the catalyst I (based on the mass of the catalyst) is Ag (silver conversion) = 14.7 mass%, Cs (Cs conversion) = 2187 mass ppm, Re (Re conversion) = 477 mass ppm, W ( W conversion) = 370 mass ppm, Cu (Cu conversion) = 465 mass ppm, Ni (Ni conversion) = 215 mass ppm.
実施例１０
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸ニッケル（ＩＩ）六水和物０．０２４ｇを添加したこと以外は、実施例１と同様にして、触媒Ｊを得た。
Example 10
In Example 1, Catalyst J was obtained in the same manner as in Example 1 except that 0.024 g of nickel (II) nitrate hexahydrate was added instead of copper (II) nitrate trihydrate. .
触媒Ｊの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１５．０質量％、Ｃｓ（Ｃｓ換算）＝２１８２質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７５質量ｐｐｍ、Ｗ（Ｗ換算）＝３６９質量ｐｐｍ、Ｎｉ（Ｎｉ換算）＝８０質量ｐｐｍであった。 The content of each component of the catalyst J (based on the mass of the catalyst) is: Ag (silver equivalent) = 15.0 mass%, Cs (Cs equivalent) = 2182 mass ppm, Re (Re equivalent) = 475 mass ppm, W ( W conversion) = 369 mass ppm and Ni (Ni conversion) = 80 mass ppm.
実施例１１
実施例１において、硝酸銅（ＩＩ）三水和物の代わりに、硝酸コバルト０．０４６ｇを添加したこと以外は、実施例１と同様にして、触媒Ｋを得た。
Example 11
In Example 1, Catalyst K was obtained in the same manner as in Example 1 except that 0.046 g of cobalt nitrate was added instead of copper (II) nitrate trihydrate.
触媒Ｋの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．５質量％、Ｃｓ（Ｃｓ換算）＝２１９１質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７８質量ｐｐｍ、Ｗ（Ｗ換算）＝３７０質量ｐｐｍ、Ｃｏ（Ｃｏ換算）＝１５１質量ｐｐｍであった。 The content of each component of the catalyst K (based on the mass of the catalyst) is as follows: Ag (silver conversion) = 14.5 mass%, Cs (Cs conversion) = 2191 mass ppm, Re (Re conversion) = 478 mass ppm, W ( W conversion) = 370 mass ppm, Co (Co conversion) = 151 mass ppm.
比較例１
実施例１において、硝酸銅（ＩＩ）三水和物を添加しなかったこと以外は、実施例１と同様にして、触媒Ｌを得た。
Comparative Example 1
In Example 1, Catalyst L was obtained in the same manner as Example 1 except that copper nitrate (II) trihydrate was not added.
触媒Ｌの各成分の含有量（触媒の質量基準）は、Ａｇ（銀換算）＝１４．７質量％、Ｃｓ（Ｃｓ換算）＝２１８７質量ｐｐｍ、Ｒｅ（Ｒｅ換算）＝４７７質量ｐｐｍ、Ｗ（Ｗ換算）＝３７０質量ｐｐｍであった。 The content of each component of the catalyst L (mass basis of the catalyst) is: Ag (silver conversion) = 14.7 mass%, Cs (Cs conversion) = 2187 mass ppm, Re (Re conversion) = 477 mass ppm, W ( W conversion) = 370 mass ppm.
上記実施例１〜１１で得られた触媒Ａ〜Ｋおよび上記比較例１で得られた触媒Ｌについて、下記方法によって、触媒性能を評価した。結果を下記表１に示す。なお、下記表１において、下記（触媒評価）方法によって算出された触媒性能を「初期触媒性能」と称する。 About the catalyst AK obtained in the said Examples 1-11, and the catalyst L obtained in the said comparative example 1, the catalyst performance was evaluated by the following method. The results are shown in Table 1 below. In Table 1 below, the catalyst performance calculated by the following (catalyst evaluation) method is referred to as “initial catalyst performance”.
（触媒評価）
上記実施例および比較例により得られた触媒Ａ〜Ｌを、それぞれ、０．６０〜０．８５ｍｍに破砕した。次に、破砕した触媒１．２ｇを、それぞれ、内径３ｍｍ、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３０容量％、酸素７．２容量％、二酸化炭素２．０容量％、ビニルクロライド２．３〜３．８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（モル％）（数式２）および初期選択率（モル％）（数式３）を算出した。
(Catalyst evaluation)
Catalysts A to L obtained in the above examples and comparative examples were each crushed to 0.60 to 0.85 mm. Next, 1.2 g of the crushed catalyst was charged into a heating type double tube stainless steel reactor having an inside diameter of 3 mm and a tube length of 300 mm, respectively, and this packed bed was filled with 30% ethylene and 7.2% oxygen. %, Carbon dioxide 2.0% by volume, vinyl chloride 2.3 to 3.8 ppm by volume, a gas consisting of nitrogen is introduced, and the ethylene conversion rate is 1.6 MPaG and the space velocity is 5500 h −1. The reaction was carried out so as to be 10 mol%. According to the following formulas 2 and 3, the conversion rate (mol%) (formula 2) and initial selectivity (mol%) (formula 3) during ethylene oxide production were calculated.
また、上記実施例、比較例で得られた触媒Ａ〜Ｌについて、下記方法によって、触媒寿命を評価した。結果を下記表１に示す。なお、下記表１において、下記（触媒寿命の評価）方法によって算出された触媒性能を「触媒寿命性能」と称する。 Moreover, about the catalyst AL obtained by the said Example and comparative example, the catalyst lifetime was evaluated by the following method. The results are shown in Table 1 below. In Table 1 below, the catalyst performance calculated by the following (evaluation of catalyst life) method is referred to as “catalyst life performance”.
（触媒寿命の評価）
触媒の寿命評価は、上記記触媒評価（初期触媒性能）を維持し、初期選択率から３モル％の選択率低下の間の選択率の低下度合い、および反応温度の上昇度合いで比較した。下記表１に、触媒１ｋｇあたりエチレンオキシド５０ｋｇを生産する間の選択率の低下度合い、および反応温度の上昇度合を、それぞれΔＳ（モル％）およびΔＴ(℃)として示した。
(Evaluation of catalyst life)
The catalyst life evaluation was performed by maintaining the above-mentioned catalyst evaluation (initial catalyst performance), and comparing the degree of decrease in selectivity between the initial selectivity and the selectivity reduction of 3 mol%, and the degree of increase in reaction temperature. Table 1 below shows the degree of decrease in selectivity during the production of 50 kg of ethylene oxide per kg of catalyst and the degree of increase in reaction temperature as ΔS (mol%) and ΔT (° C.), respectively.
上記表１に示される初期性能結果から、本発明の触媒は、比較例の触媒に比して、反応温度が有意に低いため、反応熱による触媒成分の移動や凝集に伴う状態変化を抑制でき、触媒の寿命を延長できることが期待できる。 From the initial performance results shown in Table 1, since the reaction temperature of the catalyst of the present invention is significantly lower than that of the catalyst of the comparative example, it is possible to suppress changes in state due to movement and aggregation of catalyst components due to reaction heat. It can be expected that the life of the catalyst can be extended.
また、本発明の触媒は、比較例の触媒に比して、長期使用後の選択率の低下及び反応温度の上昇度合いが有意に抑えられることがわかる。これから、本発明の触媒は、触媒寿命を有意に向上（延長）できると、考察される。ゆえに、本発明の触媒を使用することによって、長期にわたって高い選択率でアルキレンオキシドを製造できることが期待される。 It can also be seen that the catalyst of the present invention can significantly suppress the decrease in selectivity and the increase in reaction temperature after long-term use, as compared with the catalyst of the comparative example. From this, it is considered that the catalyst of the present invention can significantly improve (extend) the catalyst life. Therefore, it is expected that alkylene oxide can be produced with high selectivity over a long period of time by using the catalyst of the present invention.
Claims (9)
前記第１共促進剤は、バナジウム、モリブデン、タングステン、および硫黄からなる群から選択される少なくとも１種であり、
前記第２共促進剤は、銅、ニッケル、鉄、およびコバルトからなる群から選択される少なくとも１種である、アルキレンオキシド製造用触媒。 A catalyst for producing alkylene oxide, comprising a carrier comprising α-alumina as a main component and carrying a catalyst component containing silver, cesium, rhenium, a first co-promoter, and a second co-promoter,
The first co-promoter is at least one selected from the group consisting of vanadium, molybdenum, tungsten, and sulfur,
The second co-promoter is at least one selected from the group consisting of copper, nickel, iron, and cobalt.
前記触媒前駆体溶液を含浸させた担体を乾燥させる段階と、
乾燥後の担体を２段階以上の焼成工程で焼成を行う段階と、
を含む、請求項１〜６のいずれか１項に記載のアルキレンオキシド製造用触媒の製造方法。 impregnating a carrier mainly composed of an α-alumina carrier with a catalyst precursor solution containing a precursor of a catalyst component;
Drying the support impregnated with the catalyst precursor solution;
Firing the dried carrier in two or more firing steps;
The manufacturing method of the catalyst for alkylene oxide manufacture of any one of Claims 1-6 containing these.
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| CN115591564B (en) * | 2021-07-09 | 2024-02-13 | 中国石油化工股份有限公司 | Method for producing shaped methane oxidative coupling catalysts, use thereof and method for producing carbon dioles |
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